CN103080150A - Catalyst for polymerizing norbornene monomers and a method for producing norbornene polymer - Google Patents

Catalyst for polymerizing norbornene monomers and a method for producing norbornene polymer Download PDF

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CN103080150A
CN103080150A CN2011800398367A CN201180039836A CN103080150A CN 103080150 A CN103080150 A CN 103080150A CN 2011800398367 A CN2011800398367 A CN 2011800398367A CN 201180039836 A CN201180039836 A CN 201180039836A CN 103080150 A CN103080150 A CN 103080150A
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norbornylene
polymerization
palladium
methyl
polymkeric substance
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CN103080150B (en
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藤部聪
黍野信幸
但马恒男
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
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    • C08F4/64041—Monoanionic ligand
    • C08F4/64048—NO

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Abstract

The invention relates to a catalyst for the polymerization of norbornene monomers containing transition metal complex (A) represented by formula (1); and a method for producing norbornene copolymers containing a monomer unit represented by formulae (2) and (3). Transition metal complex (A) is preferably ([pi-allyl) {2- [N- (2,6-diisopropylphenyl ) iminomethyl ] phenolate } palladium, (pi-allyl) {2- [N- (2, 6-diisopropylphenyl) iminomethyl] -4-fluorophenolate } palladium, (pi-allyl) [2-(N-phenyliminomethyl ) phenolate] palladium and (pi-allyl ) {2- [N-(2, 6-diisopropylphenyl ) iminomethyl] -6-methylphenolate}palladium.

Description

The catalyzer and the method for preparing norbornene polymer that are used for the norbornene monomer polymerization
Technical field
The present invention relates to a kind of catalyzer, a kind of by using the preparation of this catalyzer to contain the method for (be total to) polymkeric substance of the norbornene monomer of polar group be used to making the norbornene monomer polymerization, and for the novel transition metal title complex of catalyzer.
Background technology
Usually, the addition polymer of the cycloolefin of norbornene polymer representative is used for the fields such as blooming at industrial organic materials as excellence aspect thermotolerance and the transparency.Have a plurality of reports: this class Progress in Catalysts for Addition Polymerization of Naphthenic thing can use the catalyzer that contains transistion metal compound such as Ti, Zr, Cr, Co, Ni and Pd to pass through the addition polymerization preparation of cycloolefin monomers.
For example, the open No.0445755 (patent document 1) of European patent has reported that number-average molecular weight surpasses 1, the addition homopolymer of 000,000 norbornylene can prepare independent norbornene monomer polymerization as Primary Catalysts and methylaluminoxane (MAO) as promotor by the transistion metal compound that use belongs to the element of periodictable 5-10 family.Yet the polymerization with more highly difficult norbornene monomer that contains polar group can not be carried out with this catalyst system, and has the misgivings of the catalyzer deactivation that causes about the impact owing to polar group.
Simultaneously, U.S. Patent No. 3,330,815 open (patent documents 2) disclose the norbornene monomer that contains polar group the addition homopolymer and with the multipolymer of norbornylene, wherein only use two (benzonitrile) palladiums of dichloro and Allylpalladium muriate dipolymer as catalyzer.Yet this patent does not report that polymkeric substance wherein has the example that surpasses 10,000 number-average molecular weight.The polymerization activity of catalyzer is also low so that the preparation method is far from industrial useful method.
In addition, Japanese Patent Publication No.3678754 (WO96/37526; Patent document 3) and JP-A-2008-31304 open (patent document 4) disclose a kind of improve the independent norbornene monomer addition polymerization that contains polar group or with the method for norbornylene copolymerization.Although these methods have been improved the molecular weight of polymerization activity and resulting polymers as catalyzer by the combination of using Allylpalladium muriate dipolymer, silver tetrafluoroborate and phosphofluoric acid silver, but they only disclose number-average molecular weight in an embodiment less than 200,000 multipolymer and do not prepare successfully that mechanical property is developed into the required number-average molecular weight of practical level is 200,000 or larger multipolymer.In the table 1 of patent document 4, number-average molecular weight (Mn) record and weight-average molecular weight (Mw) record replace mutually.Obviously Mw/Mn value should be approximately 2.5, and if the data in the obvious suitably interpret table 1, then do not exist number-average molecular weight to surpass 200,000 multipolymer.
Opposite with these methods, international open No.WO06/064814 (US2009/264608; Patent document 5) disclose the norbornylene that contains polar group and norbornylene addition copolymerization can by use belong to periodictable 8-10 family transition metal compound as Primary Catalysts with can make up by the promotor that produces the cationic transition metal compound with the Primary Catalysts reaction and effectively carry out, obtain thus having the multipolymer of high molecular.Yet, the disclosed norbornene compound of this publication has the structure of wherein ester group directly being introduced in the norbornylene skeleton, and because the distance between carbon-to-carbon double bond position and the polar group is short, norbornene compound transition metal complex easy and as catalyzer forms coordinate bond, causes the catalyzer deactivation.Therefore, the method can prepare the polymkeric substance with high reactivity and high molecular in independent norbornylene addition polymerization.Yet, have in use in the situation of norbornene monomer of polar monomer, the multipolymer that obtains having high molecular, but the catalyst activity of multipolymer is low.
One of method of the catalyzer deactivation that causes as the coordination bonding that prevents owing to norbornylene and transition metal complex can prolong the distance between polymerizable carbon-to-carbon double bond and the polar group (ester group).For example to disclose a kind of be 100 by using N-heterocycle carbine complex preparation number-average molecular weight to " J.Organomet.Chem.; 2009; 694; 297-303 page or leaf " (non-patent document 1), 000 or the situation of the homopolymer of larger norbornene compound, wherein a methene chain is introduced between norbornylene skeleton and the ester group.Yet the polymerization activity in the method is very low, and method is failed to obtain number-average molecular weight and surpassed 200,000 polymkeric substance.
From the description of these prior art files, can find out can be in the addition polymerization of the independent norbornene monomer that contains polar group or contain obtain in the addition copolymerization of norbornene monomer of polar group number-average molecular weight up to 200,000 or larger multipolymer and the high-activity catalyst systems of described system experience deactivation seldom be previous unknown.
As discussed above, contain in the method for addition (being total to) polymkeric substance of the norbornylene of polar group in preparation, there is not the previous situation of the high activated catalyst of norbornylene (being total to) polymkeric substance that can obtain having the mechanical property put into practice.Therefore, need this catalyzer of exploitation.
Prior art
[patent document]
The open No.0445755 of [patent document 1] European patent
[patent document 2] U.S. Patent No. 3,330,815
[patent document 3] Japanese Patent No.3678754
[patent document 4] Japanese Patent Publication No.2008-31304
[patent document 5] international open No.WO06/064814
[non-patent document]
[non-patent document 1] J.Organomet.Chem., 694, the 297-303 pages or leaves (2009)
Summary of the invention
[the problem to be solved in the present invention]
The purpose of this invention is to provide a kind of high-activity catalyst systems, this system can prepare high molecular addition (being total to) polymkeric substance of the norbornene monomer that contains polar group, and a kind of method that effectively prepares this multipolymer.
[method of dealing with problems]
As the result to the further investigation that overcomes the above problems, the inventor find to have the high molecular addition copolymer of the norbornene monomer of polar group can be effectively by with following component in conjunction with preparing: use and contain π-allyl group (η 3-allyl group) the catalyzer group of the transition metal complex of part and bidentate salicylaldimine ligand is as Primary Catalysts, wherein methene chain is introduced between norbornylene skeleton and the ester group norbornene compound that separates with polymerisable carbon-to-carbon double bond and polar group (ester group), and finished the present invention.
That is, the present invention relates to be used in [1] as mentioned below-[6] catalyzer of the polymerization of norbornene monomer; [7]-[10] in for the preparation of the method for norbornene copolymer, the norbornene copolymer in [11], and the palladium complex in [12]-[15].
[1] a kind of catalyzer of the polymerization for norbornene monomer, it contains the transition metal complex (A) of formula (1) expression:
Figure BDA00002837721200041
(in formula, M represents to be selected from a kind of transition metal of the element of 8,9 or 10 families that belong to table 1991 annual cycles, and R 1, R 2, R 3And R 4Represent independently of each other hydrogen atom; Have 1-20 carbon atom and can contain substituent alkyl; Halogen atom; Alkoxyl group; Aryloxy; Silyl with 1-20 carbon atom; The siloxy-that contains the alkyl with 1-20 carbon atom; Nitro; Cyano group; The amide group that contains the alkyl with 1-10 carbon atom; Or contain the dialkyl amido of the alkyl with 1-10 carbon atom; R 1, R 2, R 3And R 4Bonding forms ring structure mutually; R 5Expression hydrogen atom or have the alkyl of 1-20 carbon atom; R 6Expression has the alkyl of 1-20 carbon atom; R 7, R 8, R 9, R 10And R 11Represent independently of each other hydrogen atom, halogen atom or have the alkyl of 1-20 carbon atom; And R 7, R 8, R 9, R 10And R 11Bonding forms ring structure mutually.)
[2] be used for the catalyzer of norbornene monomer polymerization described in above [1], wherein in formula (1), M represents palladium (Pd) or nickel (Ni); R 5The expression hydrogen atom; R 6Expression can contain substituent phenyl; And R 7, R 8, R 9, R 10And R 11All represent hydrogen atom.
[3] be used for the catalyzer of norbornene monomer polymerization described in above [2], wherein in formula (1), M represents palladium; R 1Expression hydrogen atom or methyl; R 2And R 4All represent hydrogen atom; R 3Expression hydrogen atom or fluorine atom; And R 6Expression phenyl or 2,6-diisopropyl phenyl.
[4] as in above [1]-[3] as described in each for the catalyzer of norbornene monomer polymerization, it comprises promotor (B) and phosphine part (C), and described promotor (B) is can be by reacting the ionic compound that produces the cationic transition metal compound with transition metal complex (A).
[5] be used for the catalyzer of norbornene monomer polymerization described in above [4], wherein promotor (B) is trityl four (pentafluorophenyl group) borate or DMA four (pentafluorophenyl group) borate.
[6] be used for the catalyzer of norbornene monomer polymerization described in above [4], wherein phosphine part (C) is tricyclohexyl phosphine, three-tertiary butyl phosphine or tri isopropyl phosphine.
[7] a kind of method for preparing norbornylene (being total to) polymkeric substance, it is included under the existence such as each described catalyzer in above [1]-[6], makes independent norbornene monomer homopolymerization or norbornene monomer copolymerization.
[8] a kind of method for preparing norbornene copolymer, it comprises makes norbornene monomer and the copolymerization in the presence of such as each described catalyzer in above [1]-[6] of other vinyl monomer.
[9] a kind of method that contains the norbornene copolymer of monomeric unit shown in formula (2) and (3) for preparing:
Figure BDA00002837721200051
(in formula, R 12Expression has the alkyl of 1-10 carbon atom; And R 13, R 14And R 15Represent independently of each other hydrogen atom or have the alkyl of 1-10 carbon atom), described method comprise make corresponding to the norbornene monomer of monomeric unit shown in formula (2) and (3) as above [1]-[6] in each described catalyzer in the presence of polymerization.
[10] as preparing the method for norbornene copolymer as described in above [9], wherein multipolymer only comprises the monomeric unit of formula (2) and (3) expression.
[11] norbornene polymer, it only comprises shown in above [9] described formulas (2) monomeric unit and has 200,000-1,000,000 number-average molecular weight (Mn).
[12] (π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl] phenol } palladium.
[13] (π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 4-fluorophenol } palladium.
[14] (π-allyl group) [2-(N-phenylimino methyl) phenol] palladium.
[15] (π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 6-methylphenol } palladium.
[16] a kind of solvent that uses the polymkeric substance of dissolved monomer and non-dissolved monomer prepares the method for norbornylene (being total to) polymkeric substance by precipitation polymerization, and wherein the solvent of precipitation polymerization contains alphatic carboxylic acid ester.
[17] as preparing the method for norbornene copolymer as described in above [16], wherein norbornylene (being total to) polymkeric substance contains monomeric unit shown in formula (2) and (3):
Figure BDA00002837721200061
(in formula, R 12Expression has the alkyl of 1-10 carbon atom; And R 13, R 14And R 15Represent independently of each other hydrogen atom or have the alkyl of 1-10 carbon atom.)
[18] as preparing the method for norbornene copolymer as described in above [17], wherein multipolymer only comprises monomeric unit shown in formula (2) and the formula (3).
[19] as preparing the method for norbornene copolymer in above [16]-[18] as described in each, wherein the solvent of precipitation polymerization contains 60 volume % or more alphatic carboxylic acid ester.
[20] as preparing the method for norbornene copolymer in above [16]-[19] as described in each, wherein alphatic carboxylic acid ester is to have the aliphatic carboxylic acid of 1-5 carbon atom and the ester of alcohol.
[21] as preparing the method for norbornene copolymer in above [16]-[20] as described in each, wherein alphatic carboxylic acid ester is carboxylic acid and the ester with alcohol of 1-5 carbon atom.
[22] as preparing the method for norbornene copolymer in above [16]-[19] as described in each, wherein alphatic carboxylic acid ester is at least a member in ethyl acetate, acetic acid (n-propyl), isopropyl acetate and the acetic acid (positive butyl ester).
[23] as preparing the method for norbornene copolymer in above [16]-[18] as described in each, wherein the solvent of precipitation polymerization contains toluene and 60 volume % or more ethyl acetate.
[invention effect]
The present invention can prepare norbornylene and the high molecular addition copolymer that contains the norbornene monomer of polar group effectively.The norbornene copolymer that obtains by the present invention has excellent performance, the for example transparency, thermotolerance, low water absorbable and electrical insulation capability, and can be used for that many application such as optical application, medical applications, electronic material are used, wrapping material are used and structural material applications.
Particularly, multipolymer can be used for optical mode goods such as lens and polarized film; The electrically insulating material of film, tape carrier, film capacitor, flexible printed circuit board etc.; With medical container such as push-through packs, infusion bag and chemical bottle; Food product pack moulded product, for example plastic packets and dish; The shell of electrical equipment; Automotive interior spare, for example inner panel; The material of construction that is used for garage, glazing etc.; Deng.
The accompanying drawing summary
Fig. 1 is gained title complex among the embodiment 1-4 1H-NMR spectrum.
Fig. 2 is gained title complex among the embodiment 1-4 13C-NMR spectrum.
Fig. 3 is gained multipolymer among the embodiment 5 1H-NMR spectrum.
Fig. 4 is the IR spectrum of gained multipolymer among the embodiment 5.
Fig. 5 is gel permeation chromatography (GPC) figure of gained multipolymer in embodiment 5 and the Comparative Examples 1.
Fig. 6 is gained homopolymer among the embodiment 34 1H-NMR spectrum.
Fig. 7 is the IR spectrum of gained homopolymer among the embodiment 34.
Fig. 8 is gel permeation chromatography (GPC) figure of gained homopolymer in embodiment 34 and the Comparative Examples 3.
Carry out pattern of the present invention
The present invention is described hereinafter in more detail.
[catalyzer that is used for the norbornene monomer polymerization]
The catalyzer that is used for the polymerization of norbornene monomer of the present invention comprises: as can be by producing the ionic compound (hereinafter can be abbreviated as " promotor (B) ") of cationic transition metal compound with transition metal complex (A) reaction, and phosphine part (C) be as optional components as basal component and promotor (B) for transition metal complex (A).
Transition metal complex (A)
Transition metal complex of the present invention (A) be characterised in that comprise have be selected from 1991 annual cycle table 8,9 or 10 families the transition metal of π-allyl group part of element, and bidentate salicylaldimine ligand.
Transition metal complex (A) as the component of the catalyzer that is used for norbornene monomer polymerization of the present invention be the transition metal complex that formula (1) represents.
Figure BDA00002837721200081
M in the formula (1) represents to be selected from a kind of transition metal of 8,9 or 10 family's elements of showing for 1991 annual cycles.Specific examples comprises iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt).Wherein, from stability and the synthetic easiness viewpoint of title complex, preferred element is cobalt, nickel, palladium and platinum, more preferably uses nickel or palladium.
R in the formula (1) 1, R 2, R 3And R 4Represent independently of each other hydrogen atom; Have 1-20 carbon atom and can contain substituent alkyl; Halogen atom; Alkoxyl group; Aryloxy; Silyl with 1-20 carbon atom; The siloxy-that contains the alkyl with 1-20 carbon atom; Nitro; Cyano group; The amide group that contains the alkyl with 1-10 carbon atom; Or contain the dialkyl amido of the alkyl with 1-10 carbon atom; And R 1, R 2, R 3And R 4Bonding forms ring structure mutually.
The specific examples that can contain the alkyl of the substituent 1-20 of a having carbon atom comprises the alkyl with 1-20 carbon atom that contains linearity or side chain, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, octyl group, 2-ethylhexyl and 2-methoxy ethyl; Cycloalkyl with 3-20 carbon atom, for example cyclopentyl, cyclohexyl, 2-methoxyl group cyclohexyl, 4-methylcyclohexyl and adamantyl; Aryl, alkaryl or aralkyl with 6-20 carbon atom, for example phenyl, naphthyl, anthryl, tolyl, xylyl, benzyl and 4-fluorophenyl.The example of halogen atom comprises chlorine atom and fluorine atom.As alkoxyl group, preferably have the alkoxyl group of 1-20 carbon atom, specific examples comprises methoxyl group, oxyethyl group, isopropoxy and sec-butoxy.The example of aryloxy comprises phenoxy group and benzyloxy.The example that contains the silyl of the alkyl with 1-20 carbon atom comprises trimethyl silyl, triethylsilyl, t-butyldimethylsilyl and t-butyldiphenylsilyl; And the example that contains the siloxy-of the alkyl with 1-20 carbon atom comprises trimethylsiloxy and silicoheptane alcoxyl base.Other example comprises nitro, cyano group, comprise the amide group of the alkyl that contains 1-10 carbon atom, contain the dialkyl amido of the alkyl with 1-10 carbon atom.Wherein, from the easiness viewpoint of synthetic compound, preferred hydrogen atom, the alkyl with 1-6 carbon atom and halogen atom, particularly preferably hydrogen atom, the alkyl with 1-3 carbon atom and fluorine atom.
R in the formula (1) 5Expression hydrogen atom or have the alkyl of 1-20 carbon atom.Specific examples comprises hydrogen atom; The alkyl with 1-20 carbon atom that contains linearity or side chain, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, octyl group and 2-ethylhexyl; Cycloalkyl with 3-20 carbon atom, for example cyclopentyl, cyclohexyl and 4-methylcyclohexyl; With the aryl with 6-20 carbon atom, alkaryl or aralkyl, for example phenyl, tolyl, xylyl and benzyl.Wherein, from the easiness viewpoint of synthetic compound, preferred hydrogen atom and the alkyl with 1-6 carbon atom, particularly preferably hydrogen atom.
R in the formula (1) 6Expression has the alkyl of 1-20 carbon atom.Specific examples comprises the alkyl with 1-20 carbon atom that contains linearity or side chain, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, octyl group and 2-ethylhexyl; Cycloalkyl with 3-20 carbon atom, for example cyclopentyl, cyclohexyl and 4-methylcyclohexyl; With the aryl with 6-20 carbon atom, alkaryl or aralkyl, for example phenyl, tolyl, xylyl, 2,6-diisopropyl phenyl and benzyl.Wherein, from the easiness of synthetic compound and the stability viewpoint of title complex, preferably have aryl and the alkaryl of 6-20 carbon atom, particularly preferably phenyl and 2,6-diisopropyl phenyl.
R in the formula (1) 7, R 8, R 9, R 10And R 11Represent independently of each other hydrogen atom, halogen atom or have the alkyl of 1-20 carbon atom, and R 7, R 8, R 9, R 10And R 11Can form ring structure by mutual bonding.Specific examples comprises hydrogen atom; Halogen atom such as fluorine atom, chlorine atom and bromine atoms; The alkyl with 1-20 carbon atom that contains linearity or side chain, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, octyl group and 2-ethylhexyl; The alkenyl with 2-20 carbon atom that contains linearity or side chain, for example vinyl and 2-propenyl; With the aryl with 6-20 carbon atom, alkaryl or aralkyl, for example phenyl, tolyl and xylyl.Wherein, from the easiness viewpoint of synthetic compound, preferred hydrogen atom, have the alkyl of 1-6 carbon atom and have the aryl of 6-10 carbon atom, particularly preferably hydrogen atom and methyl.
The below provides the specific examples of transition metal complex (A) shown in the formula (1), but transition metal complex (A) is not limited to this.In the following stated specific examples, " M " has the implication identical with " M " in the formula (1).Me, Et, t-Bu and Ph also represent respectively methyl, ethyl, the tertiary butyl and phenyl.
Figure BDA00002837721200101
Figure BDA00002837721200111
Figure BDA00002837721200121
Wherein, (π-allyl group) { 2-[N-(2, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium, (π-allyl group) { 2-[N-(2, the 6-diisopropyl phenyl) iminomethyl]-the 4-fluorophenol } palladium, (π-allyl group) [2-(N-phenylimino methyl) phenol] palladium and (π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-6-methylphenol } palladium is preferred in the present invention.
Then, the following describes and prepare wherein that M is the method for the transition metal complex of the present invention of palladium.Transition metal complex of the present invention can be to prepare similarly when being different from the transition metal of palladium with M.
Transition metal complex of the present invention (A) can prepare by the ligand exchange reaction of (π-allyl group) palladium (II) as the salicylic alidehyde imine compound of precursor and following formula:
(the R in the formula 1, R 2, R 3, R 4, R 5And R 6Have with formula (1) in identical implication).Concrete preparation method's example can pass through J.Organomet.Chem., the disclosed method illustration of 1974,81,227-246.
There is not particular restriction in (π-allyl group) palladium (II) compound, and condition is that this compound contains the part that can carry out with the ligand exchange reaction of salicylic alidehyde imine compound.For example, preferred two (π-allyl groups) two (μ-chlorine), two palladiums and (π-allyl group) (methyl ethyl diketone) palladium.
The below provides the specific examples for the preparation of the salicylic alidehyde imine compound of transition metal complex (A), but the salicylic alidehyde imine compound is not limited to this.
Figure BDA00002837721200141
For this salicylic alidehyde imine compound, commercially available those can directly use.Also can use by Organometallics, 1998,17,3149-3151 page or leaf or Organometallics, 1998,17, the compound of the described method preparation of 3460-3465 page or leaf.
Above-mentioned ligand exchange reaction can be by adding salicylic alidehyde imine compound or the salicylic alidehyde imine compound that has as required the alkali of adding in (π-allyl group) palladium (II) compound as precursor be dissolved in the solvent, stirs predetermined time thereafter under preset temperature and carry out.
There is not particular restriction in the solvent that is used for ligand exchange reaction, and condition is that this solvent is not reactive for each matrix, and example comprises aliphatic hydrocrbon such as pentane, hexane and heptane; Clicyclic hydrocarbon such as hexanaphthene; Aromatic hydrocarbon such as benzene, toluene and dimethylbenzene; Halohydrocarbon such as methylene dichloride, chloroform and chlorobenzene; Nitrogen-containing hydrocarbons such as Nitromethane 99Min., oil of mirbane and acetonitrile; With ether such as diethyl ether, two
Figure BDA00002837721200151
Alkane and tetrahydrofuran (THF).In these solvents two or more can be used with mixture.The preferred solvent that stands to dewater with deuterate that uses.
There is not particular restriction in consumption to solvent, and condition is its indistinctively delayed response, and consumption can be depending on as (π-allyl group) palladium (II) compound of precursor etc. and suitably determines.Usually based on (π-allyl group) palladium (II) compound of 1g as precursor, use the 1-100g solvent.
There is not particular restriction in polymerization temperature, but temperature is generally-100 to 150 ℃, preferred-50 to 120 ℃.If temperature is lower than-100 ℃, then it reduces rate of polymerization.If temperature is higher than 150 ℃, then it causes the title complex that produces to decompose in some cases.Rate of polymerization can be controlled by selective polymerization temperature in above-mentioned scope.
Reaction times is not subjected to particular restriction, and for example is 1 minute to 50 hours.Also preferably under inert gas atmosphere such as nitrogen, react.
After reaction is finished, can with target transition metal complex (A) by generally separate/purification operations separates.Particularly, target transition metal complex (A) by centrifugal and remove by filter the salt that forms in the reaction, made thereafter the salt recrystallize and separates.
Whether target transition metal complex (A) can pass through the proofs such as NMR spectrum, mass spectrum, x-ray crystal analysis to the product that obtains by reaction.
Therefore gained transition metal complex (A) is with acting on the catalyst component that makes the norbornene monomer polymerization.
Can be for containing at least one transition metal complex (A) member's compound although be used for the catalyzer of the polymerization of norbornene monomer of the present invention, but preferred catalyst further contains promotor (B) and the phosphine part (C) of promising ionic compound, described ionic compound can be by producing the cationic transition metal compound with transition metal complex (A) reaction, and it can demonstrate the catalyst activity of enhancing.
Promotor (B)
Used among the present invention can be by comprising the ionic compound that non-coordination anion and positively charged ion are combined with example that transition metal complex (A) reaction produces the promotor (B) of cationic transition metal compound.
The example of non-coordination anion comprises the quaternary negatively charged ion of 13 family's elements of table 1991 annual cycles.Specific examples comprises four (phenyl) borate, four (fluorophenyl) borate, four (difluorophenyl) borate, four (trifluorophenyl) borate, four (tetrafluoro phenyl) borate, four (pentafluorophenyl group) borate, four (trifluoromethyl phenyl) borate, four [3,5-two (trifluoromethyl) phenyl-boron dihydroxide root, four (trityl) borate, four (xylyl) borate, triphenyl (pentafluorophenyl group) borate, [three (pentafluorophenyl group) phenyl] borate and ten Trihydrides-7,8-two carbon 11-borate.
Above-mentioned cationic example comprises carbon
Figure BDA00002837721200161
Positively charged ion, oxygen Positively charged ion, ammonium cation,
Figure BDA00002837721200163
Positively charged ion, suberyl triolefin positively charged ion and have the ferrocene cation of transition metal.
Carbon
Figure BDA00002837721200164
Cationic specific examples comprises trisubstituted carbon
Figure BDA00002837721200165
Positively charged ion, for example triphenylcarbenium Positively charged ion and trisubstd phenyl carbon
Figure BDA00002837721200167
Positively charged ion.Trisubstd phenyl carbon
Figure BDA00002837721200168
Cationic specific examples comprises three (aminomethyl phenyl) carbon
Figure BDA00002837721200169
Positively charged ion and three (3,5-dimethylphenyl) carbon
Figure BDA000028377212001610
Positively charged ion.
Oxygen
Figure BDA000028377212001611
Cationic specific examples comprises alkyl oxygen Positively charged ion such as hydronium(ion) positively charged ion and methyl oxygen
Figure BDA000028377212001613
Positively charged ion, dialkyl group oxygen
Figure BDA000028377212001614
Positively charged ion such as dimethyl oxygen Positively charged ion, and trialkyl oxygen Positively charged ion such as trimethylammonium oxygen
Figure BDA000028377212001617
Positively charged ion and triethyl oxygen
Figure BDA000028377212001618
Positively charged ion.
The specific examples of ammonium cation comprises trialkyl ammonium positively charged ion such as trimethyl ammonium positively charged ion, triethyl ammonium positively charged ion, tripropyl ammonium cation, tributyl ammonium positively charged ion, three (normal-butyl) ammonium cation; And N, N-dialkyl benzene ammonium cation such as N, N-diethylbenzene ammonium cation, N, N-2,4,6-pentamethylbenzene ammonium cation; With the dialkyl ammonium positively charged ion such as two (sec.-propyl) ammonium cations and dicyclohexyl ammonium cation.
Cationic specific examples comprises triaryl
Figure BDA000028377212001620
Positively charged ion, for example triphenyl
Figure BDA000028377212001621
Positively charged ion, three (aminomethyl phenyl)
Figure BDA000028377212001622
Positively charged ion and three (3,5-dimethylphenyl)
Figure BDA000028377212001623
Positively charged ion.
The specific examples of ferrocene cation comprises dialkylferrocene positively charged ion such as ferrocene cation, 1,1-dimethyl ferrocene positively charged ion and 1,1-diethyl ferrocene cation.
The specific examples of promotor (B) is trityl four (pentafluorophenyl group) borate, triphenylcarbenium Four (fluorophenyl) borate, N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate, trityl four [3,5-two (trifluoromethyl) phenyl] borate, N, N-dimethyl puratized agricultural spray four [3,5-two (trifluoromethyl) phenyl] borate and 1,1 '-dimethyl ferrocene four (pentafluorophenyl group) borate.
Phosphine part (C)
Used phosphine part (C) trivalent phosphorous compound that three substituting groups being independently selected from hydrogen atom, alkyl or aryl form of serving as reasons among the present invention.Specific examples comprises trialkyl phosphine, for example trimethyl-phosphine, triethyl phosphine, tri isopropyl phosphine and three-tertiary butyl phosphine; With the tricyclic alkyl phosphine, for example three cyclopentyl phosphines, tricyclohexyl phosphine; With triaryl phosphine such as triphenylphosphine.Wherein from strengthening the viewpoint of catalytic activity, preferred tricyclohexyl phosphine, three-tertiary butyl phosphine and tri isopropyl phosphine.
In the present invention, title complex is as transition metal complex (A), wherein R shown in the use formula (1) 1, R 2, R 3And R 4Expression hydrogen atom, methyl or halogen atom; R 5The expression hydrogen atom; R 6The phenyl that the expression alkyl replaces, and all R 7, R 8, R 9, R 10And R 11The expression hydrogen atom, DMA four (pentafluorophenyl group) borate { [Ph (Me) 2NH] [B (C 6F 5) 4] or trityl four (pentafluorophenyl group) borate { [Ph 3C] [B (C 6F 5) 4] as promotor (B); And tri isopropyl phosphine or three-tertiary butyl phosphine are one of the preferred embodiment that can produce the catalyzer of the norbornene polymer with high catalytic activity as the catalyzer of phosphine part (C).
In addition, title complex is as transition metal complex (A), wherein R shown in the use formula (1) 1And R 3Expression methyl or fluorine atom; R 2, R 4And R 5The expression hydrogen atom; R 6Expression phenyl or 2,6-diisopropyl phenyl; And all R 7, R 8, R 9, R 10And R 11The expression hydrogen atom, DMA four (pentafluorophenyl group) borate { [Ph (Me) 2NH] [B (C 6F 5) 4] as promotor (B); And tri isopropyl phosphine is the most preferred embodiment that can produce the catalyzer of the norbornene polymer with high catalytic activity as the catalyzer of phosphine part (C).
The use ratio of transition metal complex in the inventive method (A) and promotor (B) depends on the condition variation and can not uniformly limit, yet, (A)/(B) ratio (mol ratio) is generally 1/0.1-1/100, preferred 1/0.5-1/50, still more preferably 1/1-1/10.
The use ratio of transition metal complex in the inventive method (A) and phosphine part (C) depends on the condition variation and can not uniformly limit, yet, (A)/(C) ratio (mol ratio) is generally 1/0.1-1/2, preferred 1/0.5-1/1.8, still more preferably 1/1-1/1.5.
There is not particular restriction in temperature when catalyst component is in contact with one another, but temperature is generally-100 to 150 ℃, preferred-50 to 120 ℃.If temperature is lower than-100 ℃, then it reduces component speed of reaction each other.If temperature is higher than 150 ℃, it causes the decomposition of each component, reduces thus catalytic activity.When catalyzer is used for polymerization, by in above-mentioned scope, selecting Contact Temperature, the molecular weight of the polymkeric substance that can control rate of polymerization, produces etc.
Each catalyst component can be mixed in the presence of solvent.Although there is not particular restriction in spendable solvent, preferably do not have with the reactive of each catalyst component and with industrial-scale production and hold facile those.The specific examples of solvent comprises aliphatic hydrocrbon such as pentane, hexane and heptane; Clicyclic hydrocarbon such as hexanaphthene; Aromatic hydrocarbon such as benzene, toluene and dimethylbenzene; Halohydrocarbon such as methylene dichloride, chloroform and chlorobenzene; Nitrogen-containing hydrocarbons such as Nitromethane 99Min., oil of mirbane and acetonitrile; With ether such as diethyl ether, two
Figure BDA00002837721200181
Alkane and tetrahydrofuran (THF).Wherein, preferred aliphatic series hydrocarbon, aromatic hydrocarbon and halohydrocarbon.In these solvents two or more can be used with mixture.
[method for preparing norbornene polymer]
Method for the preparation of norbornene polymer of the present invention is characterised in that the addition polymerization of norbornene monomer in the presence of the catalyzer that is used for polymerization of the present invention.
Preparation method of the present invention is a kind of in the following method: the method that (i) obtains the addition homopolymer of norbornene monomer by independent class of norbornene monomer addition polymerization, (ii) by two classes or more multiclass norbornene monomer addition copolymerization obtain the method for the addition copolymer of norbornene monomer, and (iii) by a class or more multiclass norbornene monomer and a class or more multiclass can obtain with other vinyl monomer addition copolymerization of norbornene monomer copolymerization the method for the addition copolymer of norbornene monomer.
Norbornene monomer
There is not particular restriction in used norbornene monomer among the present invention, and condition is that it is the compound that contains norbornylene ring structure (hereinafter can referred to as " norbornylene ").This compound can contain polarity or nonpolar substituting group and can contain the ring structure that is different from the norbornylene ring.
As norbornylene, compound is preferred shown in the formula (4).
Figure BDA00002837721200182
In formula, R 16-R 19Represent independently of one another hydrogen atom; Halogen atom; The functional group of containing nitrogen-atoms, Sauerstoffatom, sulphur atom, halogen atom or Siliciumatom; With the alkyl with 1-20 carbon atom that can contain halogen atom or above-mentioned sense.R 16-R 19Also bonding forms ring each other.N is 0 or 1.
Norbornylene shown in the formula (4) can be categorized as dicyclo [2.2.1] hept-2-ene", and wherein n is 0, and Fourth Ring [6.2.1 3,6.0 2,7] 12 carbon-4-alkene, wherein n is 1.Any can be used among the preparation method of the present invention in them.
R in the formula (4) 16-R 19Specific examples comprise hydrogen atom; Halogen atom such as chlorine atom, bromine atoms and fluorine atom; The functional group such as hydroxyl, alkoxyl group, aryloxy, carbonyl, hydroxycarbonyl group, alkoxy carbonyl and the aryloxycarbonyl that contain Sauerstoffatom; Contain the functional group of nitrogen-atoms such as amino, alkylamino, arylamino, aminocarboxyl, alkyl amino-carbonyl, aromatic yl aminocarbonyl and cyano group; The functional group such as sulfydryl, alkoxyl group sulfenyl and the aryloxy sulfenyl that contain sulphur atom; With the functional group of containing Siliciumatom such as silyl, alkyl silyl, aryl silyl, alkoxysilyl and aryloxymethyl silylation.Example also comprises the alkyl with 1-20 carbon atom such as alkyl, alkenyl and the aryl that can contain these functional groups.In addition R 16-R 19Bonding forms ring mutually, and the example of this situation comprises acid anhydride structure, carbonic ether structure and dithiocarbonic acid ester structure.
The specific examples of used norbornylene comprises dicyclo [2.2.1] hept-2-ene" that is not substituted or has alkyl among the present invention, for example 2-norbornylene, 5-methyl-2-norbornylene, 5-ethyl-2-norbornylene, 5-normal-butyl-2-norbornylene, 5-n-hexyl-2-norbornylene, the positive decyl of 5--2-norbornylene, 5-cyclohexyl-2-norbornylene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornylene, 5-phenyl-2-norbornylene, 5-benzyl-2-norbornylene, Dicyclopentadiene (DCPD), dihydro Dicyclopentadiene (DCPD), Fourth Ring [9.2.1.0 2,10.0 3,8] 14 carbon-3,5,7,12-tetraene, Fourth Ring [10.2.1.0 2,11.0 4,9] 15 carbon-4,6,8, the 13-tetraene;
Be not substituted or have the Fourth Ring [6.2.1.1 of alkyl 3,6.0 2,7] 12 carbon-4-alkene, for example Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-ethyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-normal-butyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-cyclohexyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-ethylidene Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-vinyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene and 9-phenyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene;
Dicyclo [2.1.1] hept-2-ene" with alkoxy carbonyl, for example 5-norbornylene-2-carboxylate methyl ester, 5-norbornylene-2-carboxylic acid, ethyl ester, 5-norbornylene-2-synthesis, 2-methyl-5-norbornylene-2-carboxylate methyl ester, 2-methyl-5-norbornylene-2-carboxylic acid, ethyl ester, 2-methyl-5-norbornylene-2-synthesis, 5-norbornylene-2,3-dicarboxylic acid methyl esters and 5-norbornylene-2, the 3-ethyl dicarboxylate; Fourth Ring [6.2.1.1 with alkoxy carbonyl 3,6.0 2,7] 12 carbon-9-alkene, for example Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-carboxylate methyl ester, Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-carboxylic acid, ethyl ester, 4-methyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-carboxylate methyl ester, Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4,5-dicarboxylic acid methyl esters and Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4, the 5-ethyl dicarboxylate;
Dicyclo [2.2.1] hept-2-ene" with hydroxycarbonyl group, for example 5-norbornylene-2-carboxylic acid and 5-norbornylene-2,3-dicarboxylic acid; Fourth Ring [6.2.1.1 with hydroxycarbonyl group 3,6.0 2,7] 12 carbon-9-alkene, for example Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-carboxylic acid and Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4, the 5-dicarboxylic acid;
Dicyclo [2.2.1] hept-2-ene" with hydroxyl, for example 2-hydroxyl-5-norbornylene, 2-methylol-5-norbornylene, 2,2-two (methylol)-5-norbornylene and 2,3-two (methylol)-5-norbornylene; Fourth Ring [6.2.1.1 with hydroxyl 3,6.0 2,7] 12 carbon-9-alkene, for example Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-is pure, Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-methyl alcohol and Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4, the 5-dimethanol;
Dicyclo [2.2.1] hept-2-ene" with acetoxyl group, for example 2-acetoxyl group-5-norbornylene, 2-acetoxy-methyl-5-norbornylene, 2,2-two (acetoxy-methyl)-5-norbornylene and 2,3-two (acetoxy-methyl)-5-norbornylene; Fourth Ring [6.2.1.1 with acetoxyl group 3,6.0 2,7] 12 carbon-9-alkene, for example 4-acetoxyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-acetoxy-methyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene and 4,5-two (acetoxy-methyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene;
Dicyclo [2.2.1] hept-2-ene" with functional group of containing nitrogen-atoms, for example 5-norbornylene-2-nitrile and 5-norbornylene-2-carboxylic acid amides; Fourth Ring [6.2.1.1 with functional group of containing nitrogen-atoms 3,6.0 2,7] 12 carbon-9-alkene, for example Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-nitrile and Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4-carboxylic acid amides;
Dicyclo [2.2.1] hept-2-ene" with halogen atom, for example 2-chloro-5-norbornylene and 2-fluoro-5-norbornylene; Fourth Ring [6.2.1.1 with halogen atom 3,6.0 2,7] 12 carbon-9-alkene, for example 4-chlorotetracyclin [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene and 4-fluorine Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene;
Dicyclo [2.2.1] hept-2-ene" with functional group of containing Siliciumatom, for example 2-trimethylammonium oxygen base-5-norbornylene, 2-trimethoxysilyl-5-norbornylene and 2-three (trimethoxy siloxy-) silyl-5-norbornylene; Fourth Ring [6.2.1.1 with functional group of containing Siliciumatom 3,6.0 2,7] 12 carbon-9-alkene, for example 4-trimethylsiloxy Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-trimethoxysilyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene, 4-three (trimethoxy siloxy-) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene;
Dicyclo [2.2.1] hept-2-ene" with acid anhydride structure, carbonic ether structure and dithiocarbonic acid ester structure, 5-norbornylene-2 for example, 3-dicarboxylic anhydride, 5-norbornylene-2,3-carbonic ether and 5-norbornylene-2,3-dithiocarbonates; With the Fourth Ring [6.2.1.1 with acid anhydride structure, carbonic ether structure and dithiocarbonic acid ester structure 3,6.0 2,7] 12 carbon-9-alkene, for example Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4,5-dicarboxylic anhydride, Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4,5-carbonic ether and Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-9-alkene-4, the 5-dithiocarbonates.
These norbornylenes can be separately or with it two or more be used in combination.
In these norbornylenes, preferably use in the present invention the norbornylene of the monomeric unit that is equivalent to formula (2) and (3) expression:
Figure BDA00002837721200211
(in formula, R 12Expression has the alkyl of 1-10 carbon atom, and R 13, R 14And R 15Represent independently of one another hydrogen atom or have the alkyl of 1-10 carbon atom.)
In formula (2) by R 12The alkyl with 1-10 carbon atom of expression can be for linearity or branching.
The example of linear alkyl comprises methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-octyl and positive decyl.
The example of branched-alkyl comprises sec.-propyl, isobutyl-, sec-butyl, neo-pentyl, isohexyl, iso-octyl and isodecyl.
From economic point of view, wherein preferably as R 12Be the linear alkyl with 1-3 carbon atom.From the viewpoint of the preparation cost of monomer, particularly preferably methyl.
R in the formula (2) 13And the R in the formula (3) 14And R 15Represent independently of each other hydrogen atom or have the alkyl of 1-10 carbon atom, and have that the alkyl of 3-10 carbon atom can be for branching.The example of these alkyl comprise be similar to above-mentioned as R 12Those of alkyl.From the viewpoint of the preparation cost of monomer, wherein preferably as R 13, R 14And R 15Be hydrogen atom.
If R 13Be hydrogen atom, then work as R as the norbornene monomer of the monomeric unit material of formula (2) expression 12When having the alkyl of 1 carbon atom, for 2-acetoxy-methyl-5-norbornylene, work as R 12When having the alkyl of 2 carbon atoms, be 2-[ethyl ketonic oxygen base) methyl]-the 5-norbornylene, work as R 12When having the alkyl of 3 carbon atoms, be 2-[(propyl group ketonic oxygen base) methyl]-the 5-norbornylene.
If R 14And R 15Be hydrogen atom, then the norbornylene as the monomeric unit material of formula (3) expression is norbornylene.
In preparation method of the present invention, use above-mentioned transition metal complex (A), promotor (B) and phosphine part (C) that the norbornene monomer polymerization can be undertaken by mass polymerization, suspension polymerization, letex polymerization, solution polymerization or precipitation polymerization.When in being aggregated in solvent, carrying out, need to use the solvent that can not adversely affect catalyst activity.The example of spendable solvent comprises aliphatic hydrocrbon such as pentane, hexane and heptane; Clicyclic hydrocarbon such as hexanaphthene; Aromatic hydrocarbon such as benzene, toluene and dimethylbenzene; Halohydrocarbon such as methylene dichloride, chloroform and chlorobenzene; Nitrogen-containing hydrocarbons such as Nitromethane 99Min., oil of mirbane and acetonitrile; Ether such as diethyl ether, two
Figure BDA00002837721200221
Alkane and tetrahydrofuran (THF); Ester such as ethyl acetate, n-propyl acetate and n-butyl acetate; Lactone such as δ-valerolactone and gamma-butyrolactone; And water.In these solvents two or more can be used with mixture.When water was used as solvent, reaction soln can use negatively charged ion, positively charged ion or nonionogenic tenside etc. to prepare with emulsified state.
Precipitation polymerization is a kind of solvent polymeric, and uses the solvent of can dissolved monomer but can not dissolve polymer.Because along with the polymerization precipitation, it has eliminated a large amount of Weak solvent of redeposition purification such as needs of methyl alcohol of being used for polymkeric substance in precipitation polymerization, this is favourable aspect production cost.
When (being total to) polymkeric substance that comprises monomeric unit shown in formula (2) and the formula (3) as the present invention prepared by precipitation polymerization, alphatic carboxylic acid ester was preferably as can dissolved monomer but can not dissolve the polymer solvent of the polymkeric substance that produces.There is not special restriction in the solvent that is used for precipitation polymerization, and condition is that this solvent contains alphatic carboxylic acid ester, and solvent can be for comprising the mixed solvent of two or more alphatic carboxylic acid esters.Polymer solvent also can contain the good solvent (for example toluene) of polymkeric substance and the degree that Weak solvent can not dissolve to the polymkeric substance that produces.As good solvent, can use the solvent of energy catalyst-solvent.In addition, use capable of being combined is different from the energy dissolved monomer of alphatic carboxylic acid ester but can not dissolves solvent such as the normal hexane of the polymkeric substance that produces.Yet when the ratio of alphatic carboxylic acid ester reduced, it can reduce operability in some cases: the polymkeric substance that namely produces may not exclusively precipitate or may not precipitate with powder type.
Alphatic carboxylic acid ester is preferably the ester of aliphatic carboxylic acid with 1-5 carbon atom and alcohol, the aliphatic carboxylic acid that more preferably has a 1-5 carbon atom and the aliphatic carboxylic acid alkyl ester with alcohol of 1-5 carbon atom, still more preferably ethyl acetate, acetic acid (n-propyl), isopropyl acetate and acetic acid (just butyl ester).
The mixed solvent that comprises two or more alphatic carboxylic acid esters is preferably the mixed solvent that comprises two members that arbitrarily are selected from ethyl acetate, acetic acid (n-propyl), isopropyl acetate and acetic acid (positive butyl ester), the more preferably mixed solvent of ethyl acetate and acetic acid (n-propyl).The mixed solvent of alphatic carboxylic acid ester and other solvent is preferably the alkyl ester conduct with 1-5 carbon atom and has the alphatic carboxylic acid ester of 1-5 carbon atom and the mixed solvent of aromatic hydrocarbon, more preferably ethyl acetate and toluene, and the mixed solvent of acetic acid (n-propyl) and toluene.
In the method for preparing the present invention's (being total to) polymkeric substance, when carrying out precipitation polymerization, use in the situation of mixed solvent of two or more alphatic carboxylic acid esters, there is not any particular restriction in ratio of mixture to each alphatic carboxylic acid ester, and can use the solvent of the alphatic carboxylic acid ester that contains any ratio.
When using the mixture of alphatic carboxylic acid ester and other solvent, the ratio of aliphatic carboxylic acid is preferably 60 volume % or larger, more preferably 80 volume % or larger.When the ratio of alphatic carboxylic acid ester during less than 60 volume %, so that the precipitation of (being total to) polymkeric substance that produces is difficult, reduce in some cases thus the recovery rate of polymkeric substance.The ratio of alphatic carboxylic acid ester means and the ratio that comprises for the total amount of all solvent compositions of the solvent of catalyst-solvent.
In the situation of the solvent when the aliphatic solvents that is usually used in general precipitation polymerization such as hexane, heptane and hexanaphthene carry out precipitation polymerization in as the method that is preparing the present invention's (being total to) polymkeric substance, the generation that is deposited in polymkeric substance of polymkeric substance is carried out simultaneously, and precipitation polymers is attached on the reactor wall and assembles, produce thus block object, this is so that can not continue to stir solvent.Therefore, although this solvent can be used as the solvent of precipitation polymerization, this solvent is compared at relative mistake aspect the operability with the situation of using alphatic carboxylic acid ester.And, when use is usually used in the solvent polymeric so that the alkylol cpd of polymer precipitation such as methyl alcohol and ethanol; Or when ketone compound such as acetone and methylethylketone (MEK), it significantly reduces the activity of polymerizing catalyst.
When carrying out precipitation polymerization in the method that is preparing the present invention's (being total to) polymkeric substance, viewpoint from the reaction efficiency of polymerization, polymer recovery etc., importantly select not dissolve the polymkeric substance that produces, do not make the surface viscosity of precipitation polymers and do not poison the solvent of catalyzer, as this solvent, alphatic carboxylic acid ester or the solvent that contains alphatic carboxylic acid ester are suitable.
Although the structure adaptability degree is affected by the molecular structure of polymkeric substance, when there be not large difference in the composition of monomer and ratio of components, the type of polymerizing catalyst etc. had relatively little impact to solubleness.Therefore, when (being total to) polymkeric substance that contains monomeric unit shown in formula (2) and the formula (3) is different from polymerizing catalyst generation of the present invention by the precipitation polymerization use, can use above-mentioned solvent.The catalyzer that contains nickel (Ni) compound or palladium (Pd) compound that can use all can make the cyclic olefins polymerization can be by alphatic carboxylic acid ester poison and not bring into play except active those.
When carrying out polymerization, Primary Catalysts (A), promotor (B) and phosphine part (C) are mixed.These order by merging is not subjected to particular restriction, condition be (A) with Primary Catalysts (A) is mixed with phosphine part (C) before promotor (B) contacts.The component of Primary Catalysts (A) and phosphine part (C) is pre-mixed and further promotor (B) added wherein to obtain response composite and composition can be added contain and remain in the solution of polymerization single polymerization monomer.Also promotor (B) can be added to contain and remain in solution, Primary Catalysts (A) and the phosphine part (C) of polymerization single polymerization monomer; Maybe the mixture of Primary Catalysts (A) and phosphine part (C) can be added and treat in the mixture solution of polymerization single polymerization monomer and promotor (B).
In the present invention, preferably in advance Primary Catalysts (A) and phosphine part (C) are mixed to contact with each other more than 1 minute, preferred approximately 30 minutes to 1 hour, then mix with promotor (B) in the reaction system that contains promotor (B) to be added; Or the mixture of Primary Catalysts (A) and phosphine part (C) added contain in the reaction system of promotor (B).This operation can demonstrate the polymerization activity of enhancing.
There is not particular restriction in polymerization temperature, but temperature is generally-100 to 150 ℃, preferred-50 to 120 ℃.If temperature is lower than-100 ℃, then it reduces rate of polymerization.If temperature is higher than 150 ℃, then it reduces catalytic activity in some cases.Rate of polymerization and molecular weight can be controlled by selective polymerization temperature in above-mentioned scope.
Polymerization time is not subjected to particular restriction, and for example is 1 minute to 100 hours.Also preferably under inert gas atmosphere such as nitrogen, react.
After polyreaction is finished, can make the norbornene polymer as reaction product stand also can separate with drying subsequently by filtering fractionation by the aftertreatment of known operation and treatment process (for example redeposition).
In the norbornene copolymer that is comprised of monomeric unit shown in formula (2) and the formula (3) by preparation method's preparation of the present invention, the content of monomeric unit is preferably 10-70 % by mole shown in the formula (2).If the content of monomeric unit is less than 10 % by mole shown in the formula (2), then the hydrophobicity of multipolymer improves, and this reduces the solubleness of multipolymer in organic solvent, makes simultaneously water-intake rate lower.On the other hand, if content surpasses 70 % by mole, then multipolymer becomes hydrophilic, and this improves the solubleness of multipolymer in organic solvent, makes simultaneously water-intake rate higher.Therefore, can control solubleness and the water-intake rate of multipolymer in organic solvent by the content of monomeric unit shown in the adjustment type (2).
In the norbornene copolymer that is formed by monomeric unit shown in formula (2) and the formula (3) by preparation method's preparation of the present invention, the content of monomeric unit is 10-80 % by mole shown in the preferred formula (2), well balanced with between the low water absorbable of realizing suitable solubility required when norbornene copolymer formation film of the present invention, the sheet etc. and multipolymer, more preferably 15-70 % by mole, most preferably 20-60 % by mole.The content of monomeric unit shown in the formula (2) can be measured in the suitable deuterate solvent by being dissolved in by the multipolymer with powder type or form membrane 1The integrated value of H-NMR spectrum is calculated.
Norbornylene (being total to) polymkeric substance by preparation method's preparation of the present invention substantially only comprises norbornylene.Yet even so, it does not get rid of the existence of trace as 1 % by mole or the 3rd monomeric unit still less, and described the 3rd monomeric unit can not affect the performance of norbornylene of the present invention (being total to) polymkeric substance.Norbornylene (being total to) polymkeric substance by preparation method's preparation of the present invention also can not destroy the effect that the present invention attempts to improve performance with the 3rd monomer copolymerization.
There is not particular restriction in the 3rd monomer, and is preferably the monomer with olefinic carbon-to-carbon double bond.Example is alpha-olefin, for example ethene, propylene, 1-butylene, 1-amylene and 1-hexene; Aromatic vinyl compound such as vinylbenzene, alpha-methyl styrene and Vinylstyrene; Chain conjugated diolefine such as 1,3-butadiene and isoprene; Vinyl ether such as ethyl vinyl ether and propyl vinyl ether; Acrylate such as methyl acrylate, ethyl propenoate and 2-EHA; With methacrylic ester such as methyl methacrylate and β-dimethyl-aminoethylmethacrylate.Wherein, particularly preferably alpha-olefin, for example ethene, propylene and 1-hexene; With aromatic vinyl compound such as vinylbenzene.
In the norbornene copolymer by preparation method of the present invention preparation, the bonding pattern of each monomeric unit depends on that polymerizing condition can or replace for random, block.In view of the enhancing of multipolymer mechanical property, random pattern is preferred.
The number-average molecular weight (Mn) of norbornylene (be total to) polymkeric substance by preparation method of the present invention preparation is preferably 50,000-2,000 according to polystyrene by gel permeation chromatography (GPC) mensuration, 000, more preferably 100,000-1,500,000.If less than 50,000, the physical strength that then (is total to) polymkeric substance becomes not enough according to the number-average molecular weight (Mn) of polystyrene.The number-average molecular weight according to polystyrene (Mn) above 2,000,000 not only reduces the dissolution with solvents degree of (being total to) polymkeric substance when forming casting films, and improves soltion viscosity, the molding processability of this reduction (being total to) polymkeric substance.Molecular weight distribution (Mw/Mn; Weight-average molecular weight/number-average molecular weight) also is preferably 1.00-4.00, more preferably 1.30-3.50, still more preferably 1.50-3.30.If (being total to) polymkeric substance has the wide molecular weight distribution scope, (being total to) then that polymers soln becomes when forming casting films may be more inhomogeneous, and this is so that be difficult to produce excellent film.
In norbornylene (being total to) polymkeric substance by preparation method's preparation of the present invention, preferably only comprise the polymkeric substance of monomeric unit shown in the formula (2):
Figure BDA00002837721200261
(symbol in the formula is same as described above).The number-average molecular weight of this polymkeric substance (Mn) is 200,000-1,000,000.When number-average molecular weight less than 200,000 o'clock, it reduces chemical resistant properties, and work as number-average molecular weight above 1,000,000 o'clock, it not only reduces the solubleness of polymkeric substance in solvent when forming casting films, and improves soltion viscosity, reduces thus the molding processability of polymkeric substance.
The saturated water absorption of norbornylene (be total to) polymkeric substance under 23 ℃ by preparation method of the present invention preparation is generally 0.001-1 quality %, preferred 0.005-0.7 quality %, still more preferably 0.01-0.5 quality %.When the saturated water absorption of (being total to) polymkeric substance is in above-mentioned scope, even under high-temperature and humidity condition, keep various optical properties such as transparency, phase differential, the homogeneity of phase differential and the dimensional precision of (being total to) polymkeric substance.Therefore, the adhesion property of product on other material is excellent and do not experience in use and peel off.And because (be total to) polymkeric substance has the excellent compatibility with additive such as antioxidant, (be total to) polymkeric substance is allowed raising interpolation degree of freedom.Above-mentioned saturated water absorption is measured by (being total to) polymkeric substance is immersed in the water 24 hours and measures the quality that improves under 23 ℃ according to the described method of JIS K7209.
The second-order transition temperature (Tg) of norbornylene (be total to) polymkeric substance by preparation method of the present invention preparation can be depending on the formation polymkeric substance monomeric unit type, ratio of components (in the situation that polymkeric substance is multipolymer) and additive existence or the variation such as do not have, but be generally 80-350 ℃, preferred 100-320 ℃, still more preferably 120-300 ℃.If Tg is below above-mentioned scope, then heat-drawn wire becomes lower, and this can cause the optical property of thermotolerance problem and gained blooming to change with the wide model of temperature ground.If Tg more than above-mentioned scope, then during the drawing process when being heated to (being total to) polymkeric substance near Tg, its improves the possibility of (being total to) polymkeric substance thermal degradation when.
Norbornylene (being total to) the polymer processing film forming that can be by forming according to the film of solution casting method will prepare by preparation method of the present invention.As solvent to be used, can use toluene, tetrahydrofuran (THF) (THF), methylene dichloride, chloroform etc.
Embodiment
Reference example and Comparative Examples are described the present invention in more detail hereinafter.The present invention never is limited to embodiment and Comparative Examples.
In each embodiment and Comparative Examples, catalyst activity is determined by following formula.Yet in Comparative Examples 6, " molar weight of the palladium " quilt " amount of nickel " in the formula replaces.
[formula 1]
The molar weight [mmole] of catalyst activity=(amount of resulting polymers (g))/palladium)
The weight-average molecular weight of resulting polymers (Mw), number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) use polystyrene to measure as reference material by gel permeation chromatography (GPC).The ratio of components of norbornylene and 5-acetoxy-methyl-2-norbornylene (being abbreviated as " ANB ") passes through in the multipolymer 1[the δ: 3.5-4.5ppm of place, peak in the H-NMR spectrum; " the COOCH of 5-acetoxy-methyl-2-norbornylene 2-" unit] and [δ: 0.5-3.0ppm; " the CH of norbornylene (being abbreviated as " NB ") and 5-acetoxy-methyl-2-norbornylene 3COO-", " CH 2-" and " CH=" unit] integration than determining.The ANB content ratio is calculated by following formula.
[formula 2]
ANB content ratio={ (molar weight of ANB unit in the polymkeric substance)/(in the polymkeric substance in the molar weight+polymkeric substance of NB unit the molar weight of ANB unit) } * 100
The performance of synthetic material in following measurement embodiment and the Comparative Examples.
1. 1H-NMR， 13C-NMR
Equipment used: JEOL EX-400 (400MHz, by JEOL, LTD. produces)
Measuring method: by sample being dissolved in the deuterate chloroform and using tetramethylsilane to measure as internal standard substance.
2.FT-IR
Equipment used:
System: Spectrum GX (by PerkinElmer, Inc. produces)
ATR:MIRacleTM (being produced by Pike Technologies)
Measuring method: by single reflection ATR method
3. gel permeation chromatography (GPC)
Equipment used:
Post: Shodex GPC K-G+KF-806L * 2 (being produced by SHOWA DENKO K.K.),
Detector: Shodex SE-61 (being produced by SHOWA DENKO K.K.),
Measuring condition
Solvent: tetrahydrofuran (THF),
Measure temperature: 40 ℃,
Flow velocity: 1.0ml/ minute,
Sample solution concentration: 1.0mg/ml,
Injection volume: 1.0 μ l,
Working curve: the universal calibration curve,
Routine analyzer: SIC480II (System Instruments, the product of Inc.)
Cyclopentadienyl (π-allyl group) palladium passes through such as Shaw.B.L., Proc.Chem.Soc., and 1960,247 described synthetic methods are synthetic.
Synthesizing of synthetic example 1:2-acetoxy-methyl-5-norbornylene:
(by Tokyo Chemical Industry Co., Ltd. produces with Dicyclopentadiene (DCPD); 759.80g, 5.747 mole), allyl acetate is (by Tokyo Chemical Industry Co., Ltd. produce, 1,457.86g, 14.561 moles) and quinhydrones (by Wako Pure Chemical Industries Co., Ltd. production, 2.25g, 0.0204 mole) and put into the autoclave that the stainless steel of 10 liter capacities is made.After the inside with reactive system replaces with nitrogen, autoclave is heated to 190 ℃, stir content with 500rpm simultaneously, and reaction was carried out 5 hours.After reaction is finished, autoclave is cooled to room temperature and content is transferred in the distillation plant to be distilled under reducing pressure.When in 0.07kPa and 48 ℃ of lower fractionation, obtain the limpid colourless liquid material of 1,306.70g.
Measurement gained liquid substance 1H-NMR spectrum proves that this material is target 2-acetoxy-methyl-5-norbornylene.The mol ratio of the exo isomer of gained 2-acetoxy-methyl-5-norbornylene and endo isomer (outer/inner) is 18/82.
Synthetic example 2:2-[N-(2,6-diisopropyl phenyl) iminomethyl] phenol synthetic
(by Tokyo Chemical Industry Co., Ltd. produces with salicylic aldehyde; 2.00g, 16.4 mmoles), (by Tokyo Chemical Industry Co., Ltd. produces 2,6-DIPA; 3.12g, 17.6 mmoles), (by Wako Pure Chemical Industries Co., Ltd. produces ethanol; 20ml) and formic acid (by Wako Pure Chemical Industries Co., Ltd. produces; 305mg, 6.63 mmoles) put into single neck flask, and reaction was at room temperature carried out 1 day, stir the mixture simultaneously.By filtering separation and be dissolved in the methyl alcohol, recrystallize is to obtain the 1.79g yellow crystals thereafter with throw out.Measurement gained crystal 1H-NMR and 13C-NMR spectrum proves that this crystal is 2-[N-(2,6-diisopropyl phenyl) iminomethyl] phenol.
Synthetic example 3:2-[N-(2,6-diisopropyl phenyl) iminomethyl]-4-fluorophenol synthetic
(by Tokyo Chemical Industry Co., Ltd. produces with 5-fluorine salicylic aldehyde; 2.01g, 14.3 mmoles), (by Tokyo Chemical Industry Co., Ltd. produces 2,6-DIPA; 2.82g, 15.9 mmoles), (by Wako Pure Chemical Industries Co., Ltd. produces ethanol; 20ml) and formic acid (by Wako Pure Chemical Industries Co., Ltd. produces; 305mg, 6.63 mmoles) put into single neck flask, and reaction was at room temperature carried out 1 day, stir the mixture simultaneously.By filtering separation and be dissolved in the methyl alcohol, recrystallize is to obtain the 2.10g yellow crystals thereafter with throw out.Measurement gained crystal 1H-NMR and 13C-NMR spectrum proves that this crystal is 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 4-fluorophenol.
Synthesizing of synthetic example 4:2-(N-phenylimino methyl) phenol
(by Tokyo Chemical Industry Co., Ltd. produces with salicylic aldehyde; 2.00g, 16.4 mmoles), (by Wako Pure Chemical Industries Co., Ltd. produces ethanol; 20ml), (by Wako Pure Chemical Industries Co., Ltd. produces aniline; 1.70g, 18.4 mmoles) and formic acid (by Wako Pure Chemical Industries Co., Ltd. production; 305mg, 6.63 mmoles) put into single neck flask, and reaction was at room temperature carried out 1 day, stir the mixture simultaneously.By filtering separation and be dissolved in the normal hexane, recrystallize is to obtain the 1.36g yellow crystals thereafter with throw out.Measurement gained crystal 1H-NMR and 13C-NMR spectrum proves that this crystal is 2-(N-phenylimino methyl) phenol.
Synthetic example 5:2-[N-(2,6-diisopropyl phenyl) iminomethyl]-6-methylphenol synthetic
6-cresotinic acid aldehyde (is produced by Sigma-Aldrich; 881mg, 6.47 mmoles), (by Tokyo Chemical Industry Co., Ltd. produces 2,6-DIPA; 1.15g, 6.49 mmoles), (by Wako Pure Chemical Industries Co., Ltd. produces ethanol; 10ml) and formic acid (by Wako Pure Chemical Industries Co., Ltd. produces; 159mg, 3.45 mmoles) put into single neck flask, and reaction was at room temperature carried out 1 day, stir the mixture simultaneously.By filtering separation and be dissolved in the ethanol, recrystallize is to obtain the 1.31g yellow crystals thereafter with throw out.
Measurement gained crystal 1H-NMR and 13C-NMR spectrum proves that this crystal is 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 6-methylphenol.
Embodiment 1:(π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) is synthetic
[title complex A-1]
After the two neck flask interior that will be equipped with three-way stopcock replace with nitrogen, 2-[N-(2 with preparation in the synthetic example 2, the 6-diisopropyl phenyl) iminomethyl] phenol (506mg, 1.80 mmole) add wherein and be dissolved in anhydrous tetrahydro furan (by Wako Pure Chemical Industries Co., Ltd. produces; 20ml).The gained mixture is being immersed in dry ice-ethanol bath and be cooled to after-78 ℃, (by Wako Pure Chemical Industries Co., Ltd. produces with the 1L hexane solution of 1.6 moles of n-Butyl Lithiums; 1.14ml, 1.82 mmoles) dropwise slowly be delivered in the mixture 5 minutes.After instillation is finished, mixture is progressively returned to room temperature.
After the two neck flask interior that are equipped with three-way stopcock that will separately prepare replaced with nitrogen, (by Wako Pure Chemical Industries Co., Ltd. produced with chlorination Allylpalladium dipolymer; 305mg, 0.834 mmole) in the flask of packing into and be dissolved in anhydrous methylene chloride (by Wako Pure Chemical Industries Co., Ltd. produces; 20ml).
Solution immersed to be cooledly to 0 ℃ ice bath and with previously prepared tetrahydrofuran (THF)/hexane mixing solutions, dropwise slowly send 5 minutes under 0 ℃, to react 2 hours.Solvent under the pressure that reduces fully distilled thereafter.(by Wako Pure Chemical Industries Co., Ltd. produces with dry toluene recently; 20ml) add wherein, after stirring thereafter, solution is stood centrifugal under nitrogen atmosphere, remove thus undesired salt and reclaim upper toluene solution.With solution condensation under the pressure that reduces, recrystallize is to obtain the 356mg yellow crystals thereafter.Measurement gained crystal 1H-NMR, 13C-NMR and IR spectrum prove that this crystal is (π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1). 1H-NMR spectrum and 13C-NMR spectrum is shown among Fig. 1 and Fig. 2.
Embodiment 2:(π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-4-fluorophenol } palladium (title complex A-2) is synthetic
[title complex A-2]
After the inside of the two neck flasks that will be equipped with three-way stopcock replaces with nitrogen, 2-[N-(2 with preparation in the synthetic example 3, the 6-diisopropyl phenyl) iminomethyl]-4-fluorophenol (503mg, 1.68 mmole) add wherein and be dissolved in anhydrous tetrahydro furan (by Wako Pure Chemical Industries Co., Ltd. produces; 10ml).The gained mixture is being immersed in dry ice-ethanol bath and be cooled to after-78 ℃, (by Wako Pure Chemical Industries Co., Ltd. produces with the 1L hexane solution of 1.6 moles of n-Butyl Lithiums; 1.10ml, 1.76 mmoles) dropwise slowly be delivered in the mixture 5 minutes.After instillation is finished, mixture-78 ℃ of lower stirrings 15 minutes, is then progressively returned to room temperature.
After the two neck flask interior that are equipped with three-way stopcock that will separately prepare replaced with nitrogen, (by Wako Pure Chemical Industries Co., Ltd. produced with chlorination Allylpalladium dipolymer; 301mg, 0.823 mmole) in the flask of packing into and be dissolved in anhydrous methylene chloride (by Wako Pure Chemical Industries Co., Ltd. produces; 10ml).
Solution immersed to be cooledly to dry ice-ethanol bath of-78 ℃ and with previously prepared tetrahydrofuran (THF)/hexane mixing solutions, dropwise slowly sent 5 minutes.Then solution temperature progressively being returned to 0 ℃ kept 90 minutes.Solvent under the pressure that reduces fully distilled thereafter.(by Wako Pure Chemical Industries Co., Ltd. produces with dry toluene recently; 20ml) add wherein, after stirring thereafter, solution is stood centrifugal under nitrogen atmosphere, remove thus undesired salt and reclaim upper toluene solution.With solution condensation under the pressure that reduces, recrystallize is to obtain the 297mg yellow crystals thereafter.Measurement gained crystal 1H-NMR and 13C-NMR spectrum proves that this crystal is (π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-4-fluorophenol } palladium (title complex A-2). 1H-NMR spectrum and 13C-NMR spectrum is shown among Fig. 1 and Fig. 2.
Embodiment 3:(π-allyl group) [2-(N-phenylimino methyl) phenol] palladium (title complex A-3) is synthetic
Figure BDA00002837721200321
[title complex A-3]
After the two neck flask interior that will be equipped with three-way stopcock replace with nitrogen, 2-(N-phenylimino methyl) phenol (329mg with preparation in the synthetic example 4,1.67 mmole) add wherein and be dissolved in anhydrous tetrahydro furan (by Wako Pure Chemical Industries Co., Ltd. produces; 10ml).The gained mixture is being immersed in dry ice-ethanol bath and be cooled to after-78 ℃, (by Wako Pure Chemical Industries Co., Ltd. produces with the 1L hexane solution of 1.6 moles of n-Butyl Lithiums; 1.10ml, 1.76 mmoles) dropwise slowly be delivered in the mixture 5 minutes.After instillation is finished, mixture-78 ℃ of lower stirrings 30 minutes, is then progressively returned to room temperature.
After the two neck flask interior that are equipped with three-way stopcock that will separately prepare replaced with nitrogen, (by Wako Pure Chemical Industries Co., Ltd. produced with chlorination Allylpalladium dipolymer; 303mg, 0.827 mmole) in the flask of packing into and be dissolved in anhydrous methylene chloride (by Wako Pure Chemical Industries Co., Ltd. produces; 10ml).
Solution immersed to be cooledly to dry ice-ethanol bath of-78 ℃ and with previously prepared tetrahydrofuran (THF)/hexane mixing solutions, dropwise slowly sent 5 minutes.Then solution temperature is returned to 0 ℃ and with solution stirring 30 minutes.Solvent under the pressure that reduces fully distilled thereafter.(by Wako Pure Chemical Industries Co., Ltd. produces with dry toluene recently; 20ml) add wherein, after stirring thereafter, solution is stood centrifugal under nitrogen atmosphere, remove thus undesired salt and reclaim upper toluene solution.With solution condensation under the pressure that reduces, recrystallize is to obtain the 87mg yellow crystals thereafter.Measurement gained crystal 1H-NMR and 13C-NMR spectrum proves that this crystal is (π-allyl group) [2-(N-phenylimino methyl) phenol] palladium (title complex A-3). 1H-NMR spectrum and 13C-NMR spectrum is shown among Fig. 1 and Fig. 2.
Embodiment 4:(π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-6-methylphenol } palladium (title complex A-4) is synthetic
Figure BDA00002837721200331
[title complex A-4]
After the two neck flask interior that will be equipped with three-way stopcock replace with nitrogen, 2-[N-(2 with preparation in the synthetic example 5, the 6-diisopropyl phenyl) iminomethyl]-6-methylphenol (495mg, 1.67 mmole) add wherein and be dissolved in anhydrous tetrahydro furan (by Wako Pure Chemical Industries Co., Ltd. produces; 10ml).The gained mixture is being immersed in dry ice-ethanol bath and be cooled to after-78 ℃, (by Wako Pure Chemical Industries Co., Ltd. produces with the 1L hexane solution of 1.6 moles of n-Butyl Lithiums; 1.10ml, 1.76 mmoles) dropwise slowly be delivered in the mixture 5 minutes.After instillation is finished, mixture-78 ℃ of lower stirrings 20 minutes, is then progressively returned to-10 ℃.
After the two neck flask interior that are equipped with three-way stopcock that will separately prepare replaced with nitrogen, (by Wako Pure Chemical Industries Co., Ltd. produced with chlorination Allylpalladium dipolymer; 303mg, 0.827 mmole) in the flask of packing into and be dissolved in anhydrous methylene chloride (by Wako Pure Chemical Industries Co., Ltd. produces; 10ml).
Solution immersed to be cooledly to dry ice-ethanol bath of-78 ℃ and with previously prepared tetrahydrofuran (THF)/hexane mixing solutions, dropwise slowly sent 5 minutes.Then solution is stirred 2 hours with reaction under-78 ℃.Solvent under the pressure that reduces fully distilled thereafter.(by Wako Pure Chemical Industries Co., Ltd. produces with dry toluene recently; 20ml) add wherein, after stirring thereafter, solution is stood centrifugal under nitrogen atmosphere, remove thus undesired salt and reclaim upper toluene solution.With solution condensation under the pressure that reduces, recrystallize is to obtain the 197mg yellow crystals thereafter.Measurement gained crystal 1H-NMR and 13C-NMR spectrum proves that this crystal is (π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-6-methylphenol } palladium (title complex A-4). 1H-NMR spectrum and 13C-NMR spectrum is shown among Fig. 1 and Fig. 2.
Embodiment 5: the addition copolymerization of norbornylene and 2-acetoxy-methyl-5-norbornylene
After the inside of the three-necked flask that will be equipped with three-way stopcock and mechanical stirrer replaced with nitrogen, (by Tokyo Chemical Industry Co., Ltd. produced with norbornylene; 4.71g, 0.050 mole) and synthetic example 1 in the 2-acetoxy-methyl-5-norbornylene (16.62g, 0.100 mole) of preparation add wherein and be dissolved in the 75ml toluene.Further to wherein adding DMA four (pentafluorophenyl group) the borate [(C be dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) and after the solution, gained solution is heated to 70 ℃.Add in this solution synthetic among the embodiment 1 that is dissolved in the 3.5ml toluene and (π-allyl group) that in another container, prepare { 2-[N-(2, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole) and tri isopropyl phosphine [P (i-C 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) catalyst solution, under 70 ℃, carried out polyreaction 30 minutes thus.To be dissolved in the separately norbornylene of preparation (Tokyo Chemical Industries Co., Ltd. production in the 5.4ml toluene thereafter; 4.71g solution 0.050ml) adds in the reaction soln, carries out thus polyreaction other 30 minutes under 70 ℃.After reaction is finished, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.Then, with reaction soln with dilution with toluene and put into a large amount of methyl alcohol so that polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 10.52g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 1052g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 916,000 number-average molecular weight (Mn) and 2.12 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 20.4 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated. 1H-NMR spectrum, IR spectrum and gel permeation chromatography (GPC) figure are shown among Fig. 3, Fig. 4 and Fig. 5.
Embodiment 6-7:
Polymerization with embodiment 5 in identical mode carry out, difference is as in the table 1 polymerization temperature being controlled at 80 ℃ and 90 ℃.
Embodiment 8-10:
Polymerization with embodiment 6 in identical mode carry out, difference is to change shown in the table 1 promotor (B) and phosphine part (C) into those.
Embodiment 11: the addition copolymerization of norbornylene and 2-acetoxy-methyl-5-norbornylene
After the inside of the three-necked flask that will be equipped with three-way stopcock and mechanical stirrer replaced with nitrogen, (by Tokyo Chemical Industry Co., Ltd. produced with norbornylene; 4.71g, 0.050 mole) and synthetic example 1 in the 2-acetoxy-methyl-5-norbornylene (16.62g, 0.100 mole) of preparation add wherein and be dissolved in the 75ml toluene.Further to wherein adding DMA four (pentafluorophenyl group) the borate [(C be dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) and after the solution, gained solution is heated to 80 ℃.{ 2-[N-(2 will to be dissolved in (π-allyl group) that synthesizes among the embodiment 1 in the 3.5ml toluene and prepare in another container, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole) and tri isopropyl phosphine [P (i-C 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) catalyst solution add in the reaction soln initiated polymerization thus.Subsequently, when in reaction soln, adding separately norbornylene (Tokyo Chemical Industries Co., the Ltd. of preparation be dissolved in the 5.4ml toluene per 30 minutes 5 times; 4.71g, 0.050ml) solution, and when per hour the interval added twice 5-acetoxy-methyl-2-norbornylene (5.00g, 0.030 mole), polyreaction amounted to 3 hours under 80 ℃.After reaction is finished, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.Then, with reaction soln with dilution with toluene and put into a large amount of methyl alcohol so that polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 33.90g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 3390g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 283,400 number-average molecular weight (Mn) and 3.12 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 19.3 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 12-14:
Polymerization with embodiment 11 in identical mode carry out, difference is that the charging of polymerization temperature and metal complexes (A), catalyzer (B) and phosphine part (C) changes shown in the table 1 those into.
Embodiment 15: the addition copolymerization of norbornylene and 2-acetoxy-methyl-5-norbornylene
After the inside of the three-necked flask that will be equipped with three-way stopcock and mechanical stirrer replaced with nitrogen, (by Tokyo Chemical Industry Co., Ltd. produced with norbornylene; 4.71g, 0.050 mole) and synthetic example 1 in the 2-acetoxy-methyl-5-norbornylene (16.62g, 0.100 mole) of preparation add wherein and be dissolved in the 75ml toluene.{ 2-[N-(2 to be dissolved in (π-allyl group) synthetic among the embodiment 1 in the 1.0ml toluene in adding, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole) and be dissolved in tri isopropyl phosphine [P (i-C in the 1.0ml toluene 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) catalyst solution after, gained solution is heated to 80 ℃.To wherein adding DMA four (pentafluorophenyl group) the borate [(C be dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) and solution, thus initiated polymerization, and polyreaction carried out under 80 ℃ 30 minutes.Subsequently, to wherein adding the separately norbornylene of preparation (Tokyo Chemical Industries Co., the Ltd. production that is dissolved in the 5.4ml toluene; 4.71g, 0.050ml) solution, and polyreaction was carried out under 80 ℃ other 30 minutes.After reaction is finished, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.Then, with reaction soln with dilution with toluene and put into a large amount of methyl alcohol so that polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 4.30g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 430g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 355,000 number-average molecular weight (Mn) and 2.84 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 17.9 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 16: the addition copolymerization of norbornylene and 2-acetoxy-methyl-5-norbornylene
After the inside of the three-necked flask that will be equipped with three-way stopcock and mechanical stirrer replaced with nitrogen, (by Tokyo Chemical Industry Co., Ltd. produced with norbornylene; 4.71g, 0.050 mole) and synthetic example 1 in the 2-acetoxy-methyl-5-norbornylene (16.62g, 0.100 mole) of preparation add wherein and be dissolved in the 75ml toluene.Further to wherein adding DMA four (pentafluorophenyl group) the borate [(C be dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) and after the solution, gained solution is heated to 60 ℃.{ 2-[N-(2 for (π-allyl group) that synthesizes among the embodiment 2 in will being dissolved in 3.5ml toluene and prepare in another container, the 6-diisopropyl phenyl) iminomethyl]-the 4-fluorophenol } palladium (title complex A-2) (4.5mg, 0.010 mmole) and tri isopropyl phosphine [P (i-C 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) catalyst solution after, polyreaction was carried out under 60 ℃ 30 minutes.Subsequently, will be dissolved in norbornylene (Tokyo Chemical Industries Co., the Ltd. production for preparing separating in the 5.4ml toluene; 4.71g solution 0.050ml) adds wherein, carries out thus polyreaction other 30 minutes under 60 ℃.After reaction is finished, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.Then, with reaction soln with dilution with toluene and put into a large amount of methyl alcohol so that polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 13.58g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 1358g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 817,000 number-average molecular weight (Mn) and 2.07 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 31.2 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 17-23:
Polymerization with embodiment 16 in identical mode carry out, difference is that the charging of polymerization temperature and promotor (B) and monomer changes shown in the table 1 those into.
Embodiment 24: the addition copolymerization of norbornylene and 2-acetoxy-methyl-5-norbornylene
Polyreaction and aftertreatment with embodiment 5 in identical mode carry out, difference is that { 2-[N-(2 with (π-allyl group), the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole) with (π-allyl group) [2-(N-phenylimino methyl) phenol] palladium (title complex A-3) (3.4mg synthetic among the embodiment 3,0.010 mmole) replace, and polymerization temperature be controlled at 80 ℃ to obtain the polymkeric substance of 17.62g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 1762g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 460,000 number-average molecular weight (Mn) and 2.28 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 27.6 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 25-29:
Polymerization with embodiment 24 in identical mode carry out, difference is that charging, polymerization temperature and the reaction times of monomer change shown in the table 1 those into.
Embodiment 30: the addition copolymerization of norbornylene and 2-acetoxy-methyl-5-norbornylene
Polyreaction and aftertreatment with embodiment 21 in identical mode carry out, difference is that { 2-[N-(2 with (π-allyl group), the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole) { 2-[N-(2 with (π-allyl group) synthetic among the embodiment 4, the 6-diisopropyl phenyl) iminomethyl]-the 6-methylphenol } palladium (title complex A-4) (4.4mg, 0.010 mmole) replaces to obtain the polymkeric substance of 19.02g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 1902g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 720,000 number-average molecular weight (Mn) and 2.20 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 25.4 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 31-33:
Polymerization with embodiment 30 in identical mode carry out, difference is that polymerization temperature and reaction times change shown in the table 1 those into.
The equal polymerization of addition of embodiment 34:2-acetoxy-methyl-5-norbornylene
After the inside of the three-necked flask that will be equipped with three-way stopcock and mechanical stirrer replaces with nitrogen, the 2-acetoxy-methyl of preparation in the synthetic example 1-5-norbornylene (16.62g, 0.100 mole) is added wherein.Further to wherein adding DMA four (pentafluorophenyl group) the borate [(C be dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) and after the solution, gained solution is heated to 80 ℃.Adding be dissolved among the embodiment 1 in the 3.5ml toluene synthetic and separately (π-allyl group) of preparation { 2-[N-(2, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole) and tri isopropyl phosphine [P (i-C 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) catalyst solution after, polyreaction was carried out under 80 ℃ 60 minutes.After reaction is finished, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.Then, with reaction soln with dilution with toluene and put into a large amount of methyl alcohol so that polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 6.59g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 659g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 208,000 number-average molecular weight (Mn) and 2.05 molecular weight distribution (Mw/Mn). 1H-NMR spectrum, IR spectrum and gel permeation chromatography (GPC) figure are shown among Fig. 6, Fig. 7 and Fig. 8.
Embodiment 35-39:
Polymerization with embodiment 34 in identical mode carry out, difference is that the type of metal complexes (A) and polymerization temperature change shown in the table 1 those into.
Embodiment 40: the addition copolymerization (precipitation polymerization) of norbornylene and 2-acetoxy-methyl-5-norbornylene
After the inside of the three-necked flask that will be equipped with three-way stopcock and mechanical stirrer replaces with nitrogen, to be dissolved in the norbornylene (9.42g in the 5.4ml toluene, 0.100 the 2-acetoxy-methyl of preparation-5-norbornylene (16.62g in solution mole) and the synthetic example 1,0.100 mole) add wherein, be dissolved in the ethyl acetate (70ml) and be heated to 80 ℃.{ 2-[N-(2 to be dissolved in (π-allyl group) synthetic among the embodiment 1 in the 3.5ml toluene in adding, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole), tri isopropyl phosphine [P (i-C 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) and DMA four (pentafluorophenyl group) borate [(C 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) and after the catalyst solution, polyreaction was carried out 1 hour under 80 ℃.Between polymerization period, polymkeric substance precipitates with the white powder form.After reaction is finished, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 12.41g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 1241g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 287,000 number-average molecular weight (Mn) and 2.18 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 20.1 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 41: the addition copolymerization (precipitation polymerization) of norbornylene and 2-acetoxy-methyl-5-norbornylene
Polymerization with embodiment 40 in identical mode carry out, difference is that polymerization temperature and reaction times change shown in the table 1 those into.
Embodiment 42: the addition copolymerization (precipitation polymerization) of norbornylene and 2-acetoxy-methyl-5-norbornylene
Polymerization with embodiment 40 in identical mode carry out, difference is that polymer solvent changes n-propyl acetate into by ethyl acetate.
Embodiment 43: the addition copolymerization (precipitation polymerization) of norbornylene and 2-acetoxy-methyl-5-norbornylene
After the inside of the three-necked flask that will be equipped with three-way stopcock, dropping funnel and mechanical stirrer replaces with nitrogen, to be dissolved in the norbornylene (6.31g in the 7.3ml toluene, 0.067 mole) the 2-acetoxy-methyl of preparation-5-norbornylene (22.11g in solution and the synthetic example 1,0.133 mole) add wherein, be dissolved in the ethyl acetate (80ml) and be heated to 80 ℃.To be dissolved in dividually in the 2-acetoxy-methyl of preparation in norbornylene (16.29g, 0.173 mole) in the 19.0ml toluene, the synthetic example 1-5-norbornylene (14.46g, 0.087 mole) and the ethyl acetate adding dropping funnel.Subsequently, { 2-[N-(2 add (π-allyl group) synthetic among the embodiment 1 that is dissolved in the 2.5ml toluene in flask, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole), tri isopropyl phosphine [P (i-C 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) and DMA four (pentafluorophenyl group) borate [(C 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) catalyst solution after, initiated polymerization thus.Between polymerization period, polymkeric substance precipitates with the white powder form.After polymerization begins 30 minutes, begin to be contained in the instillation of the mixing solutions in the dropping funnel, and in 80 minutes, finish, polyreaction is carried out under 80 ℃ simultaneously.After instillation is finished, polyreaction was carried out other 10 minutes under 80 ℃.After polymerization begins 2 hours, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 36.10g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 3610g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 420,800 number-average molecular weight (Mn) and 2.77 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 39.0 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 44: the addition copolymerization (precipitation polymerization) of norbornylene and 2-acetoxy-methyl-5-norbornylene
Polymerization with embodiment 43 in identical mode carry out, difference is the norbornylene (27.12g in the 31.0ml toluene of being dissolved in that will be contained in the dropping funnel, 0.288 mole), the 2-acetoxy-methyl of preparation-5-norbornylene (23.94g in the synthetic example 1,0.144 mole) and the mixing solutions of ethyl acetate (135ml) was dropwise sent 140 minutes and after instillation is finished, polyreaction was further carried out 10 minutes, so that the reaction times is for amounting to 3 hours under 80 ℃.Obtain the polymkeric substance of 54.00g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 5400g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 402,800 number-average molecular weight (Mn) and 3.22 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 34.1 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 45: the addition copolymerization (precipitation polymerization) of norbornylene and 2-acetoxy-methyl-5-norbornylene
Polymerization with embodiment 43 in identical mode carry out, difference is the norbornylene (38.04g in the 44.0ml toluene of being dissolved in that will be contained in the dropping funnel, 0.404 mole), 2-acetoxy-methyl-5-norbornylene (33.58g, 0.202 mole) and the mixing solutions of ethyl acetate (190ml) was dropwise sent 200 minutes and after instillation is finished, polyreaction was further carried out 10 minutes, so that the reaction times is for amounting to 4 hours under 80 ℃.Obtain the polymkeric substance of 68.10g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 6810g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 332,300 number-average molecular weight (Mn) and 3.33 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 38.9 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Embodiment 46: the addition copolymerization of norbornylene and 2-acetoxy-methyl-5-norbornylene (using the normal hexane solvent polymeric)
After the inside of the three-necked flask that will be equipped with three-way stopcock and mechanical stirrer replaced with nitrogen, (by Tokyo Chemical Industries Co., Ltd. produced with norbornylene solution; 4.71g, 0.050 mole) and synthetic example 1 in the 2-acetoxy-methyl-5-norbornylene (16.62g, 0.100 mole) of preparation add wherein and be dissolved in the 100ml normal hexane.Further adding DMA four (pentafluorophenyl group) the borate [(C that is dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (by Strem Chemicals, Inc. produces; 8.0mg, 0.010 mmole) and after the solution, gained solution is heated to 90 ℃.To wherein add synthetic among the embodiment 1 be dissolved in the 3.5ml toluene and (π-allyl group) that in another flask, prepare { 2-[N-(2, the 6-diisopropyl phenyl) iminomethyl] phenol } palladium (title complex A-1) (4.3mg, 0.010 mmole) and tri isopropyl phosphine [P (i-C 3H 7) 3] (by Strem Chemicals, Inc. produces; 1.6mg, 0.010 mmole) catalyst solution after, polyreaction was carried out under 90 ℃ 30 minutes.Although immediately with the form precipitation of white solid, throw out is owing to the viscosity of solid surface is attached on the inwall of flask after polymerization begins for polymkeric substance.Subsequently, (by Tokyo Chemical Industries Co., Ltd. produces will to be dissolved in the norbornylene for preparing separating in the 5.4ml toluene; 4.71g, 0.050 mole) and solution adds in the reaction soln and polyreaction further carried out 30 minutes under 90 ℃.At this moment, polymkeric substance becomes grume, and it snarls agitating vane.After reaction is finished, will add along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.Then, polymkeric substance dissolves by adding toluene and solution is put into a large amount of methyl alcohol, makes thus polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 12.10g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 1210g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 214,000 number-average molecular weight (Mn) and 2.46 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 24.3 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Comparative Examples 1: the addition copolymerization (according to the polymerization of patent document 4 methods) of norbornylene and 2-acetoxy-methyl-5-norbornylene
After the inside of the two neck flasks that will be equipped with three-way stopcock replaces with nitrogen, the 2-acetoxy-methyl of preparation in the synthetic example 1-5-norbornylene (14.13g, 0.085 mole) is added wherein and be dissolved in the 50ml toluene.With this order dividually further to wherein adding the allyl palladium chloride dipolymer [[(C be dissolved in the 1ml toluene 3H 5) PdCl] 2] (by Wako Pure Chemical Industries Co., Ltd., 9mg, 0.025 mmole) solution, be dissolved in the tricyclohexyl phosphine [P (C in the 1ml toluene 6H 11) 3] (produced by Strem Chemicals Inc.; 14mg, 0.050 mmole) solution and DMA four (pentafluorophenyl group) the borate [(C that is dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] after (being produced 60mg, 0.075 mmole by Strem Chmicals Inc.) solution, immerse flask in the oil bath and be heated to 90 ℃, stir simultaneously.(by Tokyo Chemical Industries Co., Ltd. produces will to be dissolved in the norbornylene for preparing separating in the 10ml toluene; 8.00g, 0.085 mole) and solution adds in the flask, initiated polymerization thus, and polyreaction was carried out under 90 ℃ 2 hours.After reaction is finished, reaction soln is put into a large amount of methyl alcohol, make thus polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 60 ℃ dry 5 hours to obtain the polymkeric substance of 19.4g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 388g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 58,000 number-average molecular weight (Mn) and 2.06 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 37.3 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
Comparative Examples 2: norbornylene and 2-acetoxy-methyl-5-norbornylene addition copolymerization (according to the polymerization of patent document 4 methods)
Polymerization with Comparative Examples 1 in identical mode carry out, difference is allyl palladium chloride dipolymer [[(C 3H 5) PdCl] 2] (4.5mg, 0.125 mmole), tricyclohexyl phosphine [P (C 6H 11) 3] (7mg, 0.025 mmole) and DMA four (pentafluorophenyl group) borate [(C 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] (30mg, 0.0375 mmole) as catalyzer, and make reaction under 60 ℃, carry out obtaining the polymkeric substance of 4.3g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 172g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 105,400 number-average molecular weight (Mn) and 1.98 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 18.2 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
The equal polymerization of addition (according to the polymerization of patent document 4 methods) of Comparative Examples 3:2-acetoxy-methyl-5-norbornylene
After the inside of the two neck flasks that will be equipped with three-way stopcock replaces with nitrogen, the 2-acetoxy-methyl of preparation in the synthetic example 1-5-norbornylene (14.13g, 0.085 mole) is added wherein and be dissolved in the 67ml toluene.With this order dividually further to wherein adding the allyl palladium chloride dipolymer be dissolved in the 1ml toluene (by Wako Pure Chemical Industries Co., Ltd., 4.5mg, 0.0125 mmole) and solution, be dissolved in the tricyclohexyl phosphine [P (C in the 1ml toluene 6H 11) 3] (produced by Strem Chemicals Inc.; 7mg, 0.025 mmole) solution and DMA four (pentafluorophenyl group) the borate [(C that is dissolved in the 1ml methylene dichloride 6H 5) (CH 3) 2NH] [B (C 6F 5) 4] after (being produced 30mg, 0.0375 mmole by Strem Chemicals Inc.) solution, immerse flask in the oil bath and be heated to 90 ℃, stir simultaneously, polyreaction was carried out 2 hours.After reaction is finished, reaction soln is put into a large amount of methyl alcohol, make thus polymer precipitation.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 60 ℃ dry 5 hours to obtain the polymkeric substance of 0.35g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 14g polymkeric substance/mmole palladium (Pd).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 26,000 number-average molecular weight (Mn) and 1.86 molecular weight distribution (Mw/Mn).
The equal polymerization of addition of Comparative Examples 4:2-acetoxy-methyl-5-norbornylene (according to the polymerization of non-patent document 1 method)
Non-patent document 1 has been described following method.Namely as general reaction conditions, this document has been described and " has been made [(1; 2; 3-η)-1; the 1-phenylbenzene-2-methyl-2-propenyl] chlorine [1; two (2,6-the diisopropyl phenyl)-2-imidazoles subunits of 3-] palladium (1.6mg, 0.0022 mmole) and four (pentafluorophenyl group) lithium tetraborate diethyl ether title complex Li[B (C that are dissolved in the chlorobenzene (3ml) 6F 5) 42.5 (C 2H 5) 2O] (3.0mg, 0.0034 mmole) at room temperature reacted under nitrogen atmosphere 8 hours.Subsequently, reaction soln is filtered by syringe filter, and filtrate is added being dissolved in 5-acetoxy-methyl in the chlorobenzene (1ml)-2-norbornylene (1.0g, 6.6 mmoles) solution of separately preparation.Then, gained solution was reacted 20 hours under preset temperature, and will wash 3 times with methyl alcohol (20ml) and further drying under vacuum by the powder (50ml) that precipitation in methyl alcohol obtains." non-patent document 1 do not have to describe the details about each preparation method; but in table 3, instructed " in [(1 of 2/1000ths the amount that 1 hour reaction times, the molar ratio computing 5-acetoxy-methyl-2-norbornylene of packing into are set, 2,3-η)-1,1-phenylbenzene-2-methyl-2-propenyl] chlorine [1, two (2,6-the diisopropyl phenyl)-2-imidazoles subunits of 3-] 1.5 times of palladium and molar ratio computings be to four (pentafluorophenyl group) lithium tetraborate diethyl ether title complex Li[B of the amount of palladium complex (C 6F 5) 42.5 (C 2H 5) 2O], use chlorobenzene to be controlled at as solvent and with temperature of reaction in 50 ℃ the situation, obtain polymkeric substance, wherein the catalytic activity based on polymer yield and catalyst charge calculating is that 123g polymkeric substance/mmole palladium (Pd) and number-average molecular weight (Mn) are 65,000 ".
The equal polymerization of addition of Comparative Examples 5:2-acetoxy-methyl-5-norbornylene (according to the polymerization of non-patent document 1 method)
Non-patent document 1 has been instructed in table 3 " 1.5 times of [(1; 2; 3-η)-1; 1-phenylbenzene-2-methyl-2-propenyl] chlorine [1; two (2,6-the diisopropyl phenyl)-2-imidazoles subunits of 3-] palladium of 2/1000ths the amount that 4 hours reaction times, the molar ratio computing 5-acetoxy-methyl-2-norbornylene of packing into are set and molar ratio computings to four (pentafluorophenyl group) lithium tetraborate diethyl ether title complex Li[B of the amount of palladium complex (C 6F 5) 42.5 (C 2H 5) 2O], use chlorobenzene to be controlled at as solvent and with temperature of reaction in 50 ℃ the situation, obtain polymkeric substance, wherein the catalytic activity based on polymer yield and catalyst charge calculating is that 60g polymkeric substance/mmole palladium (Pd) and number-average molecular weight (Mn) are 126,000 ".
Comparative Examples 6: the 2-acetoxy-methyl of use Ni catalyzer-5-norbornylene addition copolymerization (precipitation polymerization)
After the 300ml volume three-necked flask inside that will be equipped with three-way stopcock and mechanical stirrer replaced with nitrogen, (by Tokyo Chemical Industries Co., Ltd. produced will to be dissolved in norbornylene in the 11.1ml toluene; 9.6g, 0.102 mole) and solution, 2-acetoxy-methyl-5-norbornylene (17.1g, 0.103 mole) and 60ml ethyl acetate (being produced by Showa Denko K.K.) add in the flask.Simultaneously, with two (methyl ethyl diketone) nickel (10.3mg, 40 micromoles), three (pentafluorophenyl group) boron [B (C 6F 5) 3] (61.0mg, 120 micromoles) and trimethyl aluminium be (by Sigma-Aldrich; 2.0M toluene solution, 0.10ml, 200 micromoles) be enclosed in the 20ml volume carboy under the nitrogen and be dissolved in the 4ml dry toluene, immediately total solution is added in the three-necked flask, thus initiated polymerization.Between polymerization period, polymkeric substance precipitates with the white powder form.Polymerization was at room temperature carried out 30 minutes and will be added along with the 8ml methyl alcohol that a small amount of hydrochloric acid adds in the reaction soln, thus termination reaction.The polymkeric substance of precipitation by filtering, is washed thereafter and separates, then under the pressure that is reducing under 90 ℃ dry 5 hours to obtain the polymkeric substance of 8.9g white powder form.Catalytic activity based on polymer yield and catalyst charge calculating is 223g polymkeric substance/mmole nickel (Ni).
Resulting polymers easily is dissolved in common solvent such as THF and the chloroform and has 687,000 number-average molecular weight (Mn) and 1.99 molecular weight distribution (Mw/Mn).By 1The ratio of components of 2-acetoxy-methyl-5-norbornene monomer unit is 26.0 % by mole in the polymkeric substance that the integrated value of H-NMR spectrum is calculated.
About embodiment 1-46 and Comparative Examples 1-6, catalyst type, polymerizing condition etc. is shown in the table 1, and polymerization result is shown in the table 2.Symbol in the table 1 has following implication separately:
Metal complexes (A):
A-1:(π-allyl group) 2-[N-(2,6-diisopropyl phenyl) iminomethyl] and phenol } palladium
A-2:(π-allyl group) 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 4-fluorophenol } palladium
A-3:(π-allyl group) [2-(N-phenylimino methyl) phenol] palladium
A-4:(π-allyl group) 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 6-methylphenol } palladium
A-5: allyl palladium chloride dipolymer
A-6:[(1,2,3-η)-1,1-phenylbenzene-2-methyl-2-propenyl] chlorine [two (2,6-the diisopropyl phenyl)-2-imidazoles subunits of 1,3-] palladium
S-1: two (methyl ethyl diketone) nickel
Promotor (B):
B-1:N, accelerine four (pentafluorophenyl group) borate,
B-2: trityl four (pentafluorophenyl group) borate,
B-3: four (pentafluorophenyl group) lithium tetraborate
B-4: three (pentafluorophenyl group) boron,
B-5: trimethyl aluminium
Phosphine part (C)
C-1: tri isopropyl phosphine,
C-2: tricyclohexyl phosphine,
C-3: three-tertiary butyl phosphine
Monomer:
NB: norbornylene,
ANB:2-acetoxy-methyl-5-norbornylene
All polymkeric substance of gained easily are dissolved in common solvent such as THF and the chloroform in embodiment 5-46 and Comparative Examples 1-3 and 6.
Table 1
Figure BDA00002837721200471
Figure BDA00002837721200481
Table 2
Figure BDA00002837721200482
Figure BDA00002837721200491
Figure BDA00002837721200501
* the molecular weight distribution among the embodiment 10 has two peaks; Value such as Mn are population mean.
Copolymerization about norbornylene and 2-acetoxy-methyl-5-norbornylene, method by patent document 4 does not produce molecular weight (Mn) above 200,000 multipolymer, and do not have confirmation to have the catalytic activity (Comparative Examples 1-2) of industrial practice purposes prospect.With the nickel in the Comparative Examples 6 (Ni) catalyst system, the multipolymer that obtains having high molecular, but the method is inadequate aspect catalytic activity.Method produced according to the present invention obtains having very good mechanical properties and surpasses the norbornene copolymer (embodiment 1-33,40-46) of 200,000 molecular weight (Mn) with the catalytic activity with industrial practice purposes prospect.
On the other hand, homopolymerization about 2-acetoxy-methyl-5-norbornene monomer, method by non-patent document 1 does not produce molecular weight (Mn) above 200,000 homopolymer, and even in the situation of molecular weight (Mn) less than 200,000 homopolymer (Comparative Examples 3), there is not to confirm to have a catalytic activity of industrial practice purposes prospect yet.The method of norbornylene homopolymer produced according to the present invention obtains having very good mechanical properties and surpasses the polymkeric substance (embodiment 34-39) of 100,000 molecular weight (Mn) with the catalytic activity with industrial practice purposes prospect.
Industrial applicibility
Norbornylene (being total to) polymkeric substance that obtains by preparation method of the present invention has excellent performance, for example transparency, thermotolerance, low water absorbable and electrical insulation capability, and can be used for the optics moulded product, for example lens and polarized film; Film, tape carrier, film capacitor, be used for the electrically insulating material of flexible printed circuit board etc.; And pharmaceutical containers, for example Blister Package, infusion bag and chemical bottle; Food product pack moulded product, for example plastics bag and dish; The shell of electrical equipment; Automotive interior accessory, for example inner panel; The material of construction of garage, glazing etc.; Deng.

Claims (15)

1. catalyzer that is used for the norbornene monomer polymerization, it contains the transition metal complex (A) of formula (1) expression:
(in formula, M represents to be selected from the transition metal of the element of 8,9 or 10 families that belong to table 1991 annual cycles, and R 1, R 2, R 3And R 4Represent independently of each other hydrogen atom; Have 1-20 carbon atom and can contain substituent alkyl; Halogen atom; Alkoxyl group; Aryloxy; Silyl with 1-20 carbon atom; The siloxy-that contains the alkyl with 1-20 carbon atom; Nitro; Cyano group; The amide group that contains the alkyl with 1-10 carbon atom; Or contain the dialkyl amido of the alkyl with 1-10 carbon atom; R 1, R 2, R 3And R 4Bonding forms ring structure mutually; R 5Expression hydrogen atom or have the alkyl of 1-20 carbon atom; R 6Expression has the alkyl of 1-20 carbon atom; R 7, R 8, R 9, R 10And R 11Represent independently of each other hydrogen atom, halogen atom or have the alkyl of 1-20 carbon atom; And R 7, R 8, R 9, R 10And R 11Bonding forms ring structure mutually.)
2. according to claim 1 the catalyzer that is used for the norbornene monomer polymerization, wherein in formula (1), M represents palladium (Pd) or nickel (Ni); R 5The expression hydrogen atom; R 6Expression can contain substituent phenyl; And R 7, R 8, R 9, R 10And R 11All represent hydrogen atom.
3. according to claim 2 the catalyzer that is used for the norbornene monomer polymerization, wherein in formula (1), M represents palladium; R 1Expression hydrogen atom or methyl; R 2And R 4All represent hydrogen atom; R 3Expression hydrogen atom or fluorine atom; And R 6Expression phenyl or 2,6-diisopropyl phenyl.
4. each the catalyzer that is used for the norbornene monomer polymerization according to claim 1-3, it comprises promotor (B) and phosphine part (C), and described promotor (B) is can be by reacting the ionic compound that produces the cationic transition metal compound with transition metal complex (A).
5. according to claim 4 the catalyzer that is used for the norbornene monomer polymerization, wherein promotor (B) is trityl four (pentafluorophenyl group) borate or DMA four (pentafluorophenyl group) borate.
6. according to claim 4 the catalyzer that is used for the norbornene monomer polymerization, wherein phosphine part (C) is tricyclohexyl phosphine, three-tertiary butyl phosphine or tri isopropyl phosphine.
7. method for preparing norbornylene (being total to) polymkeric substance, it is included under the existence such as each described catalyzer among the claim 1-6, makes independent norbornene monomer homopolymerization or norbornene monomer copolymerization.
8. method for preparing norbornene copolymer, it comprise norbornene monomer and other vinyl monomer in such as claim 1-6 each described catalyzer in the presence of copolymerization.
9. one kind prepares the method that contains the norbornene copolymer of monomeric unit shown in formula (2) and (3):
(in formula, R 12Expression has the alkyl of 1-10 carbon atom; And R 13, R 14And R 15Represent independently of each other hydrogen atom or have the alkyl of 1-10 carbon atom), described method comprise the norbornene monomer that makes corresponding to monomeric unit shown in formula (2) and (3) in such as claim 1-6 each described catalyzer in the presence of polymerization.
10. according to claim 9 the method for preparing norbornene copolymer, wherein said multipolymer only comprises the monomeric unit of formula (2) and (3) expression.
11. norbornene polymer, it only comprises monomeric unit shown in the formula as claimed in claim 9 (2) and has 200,000-1,000,000 number-average molecular weight (Mn).
(12. π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl] phenol } palladium.
(13. π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 4-fluorophenol } palladium.
(14. π-allyl group) [2-(N-phenylimino methyl) phenol] palladium.
(15. π-allyl group) { 2-[N-(2,6-diisopropyl phenyl) iminomethyl]-the 6-methylphenol } palladium.
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